Amphiphilic block polymers prepared by alkene

ABSTRACT

The invention relates to a multiblock polyolefin, and methods to make a multiblock polyolefin, represented by the formula (X) or (XII):
 
PO—C(R 11 )(R 12 )—C(R 13 )═C(R 14 )—C(O)—O—((CR 15 R 16 ) z —(CR 17 R 18 ) m —O) n —R 19   (X)
 
or
 
PO—C(R 11 )(R 12 )—C(R 13 )═C(R 14 )—C(O)—O—((CR 15 R 16 ) z —(CR 17 R 18 ) m O) n —C(O)—C(R 14 )═C(R 13 )—C(R 12 )(R 11 )—PO  (XX),
 
wherein R 11 , R 12 , R 13 , and R 14  are each independently a substituted or unsubstituted C 1  through C 4  hydrocarbyl group or a hydrogen; R 15 , R 16 , R 17 , and R 18  are each independently a substituted or unsubstituted C 1  through C 4  hydrocarbyl group or a hydrogen; R 19  is a C 1  to a C 20  substituted or unsubstituted hydrocarbyl group or a hydrogen; z is ≧1 to about 5; m is ≧1 to about 5; PO is a polyolefin hydrocarbyl group comprising 10 to 4000 carbon atoms; and n is from 1 to about 10,000.

PRIORITY CLAIM

This application is a divisional of and claims priority to U.S. Ser. No.13/072,261 filed Mar. 25, 2011.

RELATED APPLICATIONS

This application is related to U.S. Ser. No. 12/143,663, filed on Jun.20, 2008 (Published as WO 2009/155471); U.S. Ser. No. 12/487,739, filedon Jun. 19, 2009 (Published as WO 2009/155472); U.S. Ser. No.12/488,066, filed on Jun. 19, 2009 (Published as WO 2009/155510);12/488,093 filed on Jun. 19, 2009 (Published as WO 2009/155517); andU.S. Ser. No. 12/642,453, filed Dec. 18, 2009; which is acontinuation-in-part application of U.S. Ser. No. 12/533,465 filed onJul. 31, 2009, which claims priority to and the benefit of U.S. Ser. No.61/136,172, filed on Aug. 15, 2008; which are all incorporated byreference herein.

FIELD OF THE INVENTION

This invention relates to ester functionalization of vinyl terminatedpolyolefins by metathesis reactions.

BACKGROUND OF THE INVENTION

Metathesis is generally thought of as the interchange of radicalsbetween two compounds during a chemical reaction. There are severalvarieties of metathesis reactions, such as ring opening metathesis,acyclic diene metathesis, ring closing metathesis, and cross metathesis.These reactions, however, have had limited success with the metathesisof functionalized olefins.

Methods for the production of polyolefins with end-functionalized groupsare typically multi-step processes that often create unwantedby-products and waste of reactants and energy.

R. T. Mathers and G. W. Coates, Chem. Commun., 2004, pp. 422-423disclose examples of using cross-metathesis to functionalize polyolefinscontaining pendant vinyl groups to form polar-functionalized productswith a graft-type structure.

D. Astruc et al., J. Am. Chem. Soc., 2008, 130, pp. 1495-1506 and D.Astruc et al., Angew. Chem. Int. Ed., 2005, 44, pp. 7399-7404 discloseexamples of using cross metathesis to functionalize non-polymericmolecules containing vinyl groups.

For reviews of methods to form end-functionalized multiblockpolyolefins, see: (a) S. B. Amin and T. J. Marks, Angew. Chem. Int. Ed.,2008, 47, pp. 2006-2025; (b) T. C. Chung, Prog. Polym. Sci., 2002, 27,pp. 39-85; and (c) R. G. Lopez, F. D'Agosto, and C. Boisson, Prog.Polym. Sci., 2007, 32, pp. 419-454.

U.S. Ser. No. 12/487,739, filed Jun. 19, 2009 discloses certain vinylterminated oligomers and polymers that are functionalized for use inlubricant applications.

U.S. Ser. No. 12/143,663, filed on Jun. 20, 2008 discloses certain vinylterminated oligomers and polymers that are functionalized in U.S. Ser.No. 12/487,739, filed Jun. 19, 2009.

Additional references of interest include U.S. Pat. No. 4,988,764.

Thus, there is a need to develop a means to provide functionalizedmultiblock polyolefins (particularly end-functionalized) by metathesisreactions, particularly reactions with good conversion, preferably undermild reaction conditions in a minimal number of steps. There is also aneed for a single reaction type that allows for a variety of functionalgroups to be added to polyolefins in an economical manner.

End-functionalized multiblock polyolefins that feature a chemicallyreactive or polar end group are of interest for use in a broad range ofapplications, such as compatibilizers, tie-layer modifiers, surfactants,and surface modifiers.

The instant invention's use of olefin alkene metathesis to introducefunctional groups is both a commercially economical and an“atom-economical” route to end functionalized multiblock polyolefins.This invention further provides vinyl-terminated polyolefins that reactwith functionalized alkenes in the presence of a metathesis catalyst toform polar end-functionalized multiblock polyolefins. Herein isdescribed a novel method for polar end functionalized multiblockpolyolefin production by the metathesis of vinyl-terminated polyolefinswith ester functionalized alkenes. This method is useful in a range ofpolyolefins, including isotactic polypropylene (iPP), atacticpolypropylene (aPP), ethylene propylene copolymer (EP), and polyethylene(PE).

SUMMARY OF THE INVENTION

This invention relates to a process to functionalize polyolefins (asused herein, polyolefin is defined to include both polymers andoligomers) comprising contacting an alkene metathesis catalyst with anacrylate or methacrylate functionalized polyalkylene glycol and one ormore vinyl terminated polyolefins.

Preferably the vinyl terminated polyolefin comprise one or more of:

a) a propylene co-oligomer having an Mn of 300 to 30,000 g/mol (asmeasured by ¹H NMR) comprising 10 to 90 mol % propylene and 10 to 90 mol% of ethylene, wherein the oligomer has at least X % allyl chain ends(relative to total unsaturations), where: 1) X=(−0.94 (mol % ethyleneincorporated)+100), when 10 to 60 mol % ethylene is present in theco-oligomer; 2) X=45, when greater than 60 and less than 70 mol %ethylene is present in the co-oligomer; and 3) X=(1.83*(mol % ethyleneincorporated)−83), when 70 to 90 mol % ethylene is present in theco-oligomer; and/or

b) a propylene oligomer, comprising more than 90 mol % propylene andless than 10 mol % ethylene, wherein the oligomer has: at least 93%allyl chain ends, an Mn of about 500 to about 20,000 g/mol (as measuredby ¹H NMR), an isobutyl chain end to allylic vinyl group ratio of 0.8:1to 1.35:1.0 and less than 1400 ppm aluminum; and/or

c) a propylene oligomer, comprising at least 50 mol % propylene and from10 to 50 mol % ethylene, wherein the oligomer has: at least 90% allylchain ends, Mn of about 150 to about 10,000 g/mol (as measured by ¹HNMR), and an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to1.3:1.0, wherein monomers having four or more carbon atoms are presentat from 0 to 3 mol %; and/or

d) a propylene oligomer, comprising at least 50 mol % propylene, from0.1 to 45 mol % ethylene, and from 0.1 to 5 mol % C₄ to C₁₂ olefin,wherein the oligomer has: at least 87% allyl chain ends (alternately atleast 90%), an Mn of about 150 to about 10,000 g/mol, (as measured by ¹HNMR), and an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to1.35:1.0; and/or

e) a propylene oligomer, comprising at least 50 mol % propylene, from0.1 to 45 mol % ethylene, and from 0.1 to 5 mol % diene, wherein theoligomer has: at least 90% allyl chain ends, an Mn of about 150 to about10,000 g/mol (as measured by ¹H NMR), and an isobutyl chain end toallylic vinyl group ratio of 0.7:1 to 1.35:1.0; and/or

f) a homooligomer, comprising propylene, wherein the oligomer has: atleast 93% allyl chain ends, an Mn of about 500 to about 20,000 g/mol (asmeasured by ¹H NMR), an isobutyl chain end to allylic vinyl group ratioof 0.8:1 to 1.2:1.0, and less than 1400 ppm aluminum; and/or

g) a branched polyolefin having an Mn (¹H NMR) of 7,500 to 60,000 g/molcomprising: (i) one or more alpha olefin derived units comprisingethylene and propylene; (ii) 50% or greater allyl chain ends, relativeto total number of unsaturated chain ends; and (iii) a g′(vis) of 0.90or less; and/or

h) branched polyolefins having an Mn greater than 60,000 g/molcomprising: (i) one or more alpha olefins comprising ethylene andpropylene; (ii) 50% or greater allyl chain ends, relative to totalunsaturated chain ends; (iii) a g′ (vis) of 0.90 or less; and (iv) abromine number which, upon complete hydrogenation, decreases by at least50%; and/or

i) a branched polyolefins having an Mn of less than 7,500 g/molcomprising: (i) one or more alpha olefin derived units comprisingethylene and propylene; (ii) a ratio of percentage of saturated chainends to percentage of allyl chain ends of 1.2 to 2.0; and (iii) 50% orgreater allyl chain ends, relative to total moles of unsaturated chainends; and/or

j) D vinyl terminated higher olefin copolymers having an Mn (measured by¹H NMR) of 300 g/mol or greater (preferably 300 to 60,000 g/mol)comprising: (i) from about 20 to 99.9 mol % of at least one C₅ to C₄₀higher olefin; and (ii) from about 0.1 to 80 mol % of propylene; whereinthe higher olefin copolymer has at least 40% allyl chain ends; and/or

k) vinyl terminated higher olefin copolymers having an Mn (measured by¹H NMR) of 300 g/mol or greater (preferably 300 to 60,000 g/mol)comprising: (i) from about 80 to 99.9 mol % of at least one C₄ olefin;and (ii) from about 0.1 to 20 mol % of propylene, wherein the higherolefin copolymer has at least 40% allyl chain ends; and/or

l) a higher olefin polymer having an Mn (measured by ¹H NMR) of at least200 g/mol comprising of one or more C₄ to C₄₀ higher olefin derivedunits, where the higher olefin vinyl terminated polymer comprisessubstantially no propylene derived units; and wherein the higher olefinpolymer has at least 5% allyl chain ends.

DETAILED DESCRIPTION

The term “polyolefin” as used herein means an oligomer or polymer of twoor more olefin mer units and specifically includes oligomers andpolymers as defined below. An “olefin,” alternatively referred to as“alkene,” is a linear, branched, or cyclic compound of carbon andhydrogen having at least one double bond. Ethylene shall be consideredan alpha-olefin.

A propylene polymer or oligomer contains at least 50 mol % of propylene,an ethylene polymer or oligomer contains at least 50 mol % of ethylene,and so on.

For purposes of this specification and the claims appended thereto, whena polymer or copolymer is referred to as comprising an olefin,including, but not limited to, ethylene, propylene, and butene, theolefin present in such polymer or copolymer is the polymerized form ofthe olefin. For example, when a copolymer is said to have an “ethylene”content of 35 wt % to 55 wt %, it is understood that the mer unit in thecopolymer is derived from ethylene in the polymerization reaction andsaid derived units are present at 35 wt % to 55 wt %, based upon theweight of the copolymer. A “polymer” has two or more of the same ordifferent mer units. A “homopolymer” is a polymer having mer units thatare the same. A “copolymer” is a polymer having two or more mer unitsthat are different from each other. A “terpolymer” is a polymer havingthree mer units that are different from each other. The term “different”as used to refer to mer units indicates that the mer units differ fromeach other by at least one atom or are different isomerically.Accordingly, the definition of copolymer, as used herein, includesterpolymers and the like. An oligomer is typically a polymer having alow molecular weight (such an Mn of less than 25,000 g/mol, preferablyless than 2,500 g/mol) or a low number of mer units (such as 75 merunits or less).

As used herein, Mn is number average molecular weight (measured by ¹HNMR unless stated otherwise), Mw is weight average molecular weight(measured by Gel Permeation Chromatography), and Mz is z averagemolecular weight (measured by Gel Permeation Chromatography), wt % isweight percent, and mol % is mole percent. Molecular weight distribution(MWD) is defined to be Mw (measured by Gel Permeation Chromatography)divided by Mn (measured by ¹H NMR). Unless otherwise noted, allmolecular weight units (e.g., Mw, Mn, Mz) are g/mol.

“Allyl chain ends” (also referred to as “vinyl termination”, “vinylchain ends” “allylic vinyl end group” or “vinyl content”) is defined tobe a polyolefin (oligomer or polymer) having at least one terminusrepresented by formula I:

where the “••••” represents the polyolefin chain. In a preferredembodiment, the allyl chain end is represented by the formula II:

The amount of allyl chain ends is determined using ¹H NMR at 120° C.using deuterated tetrachloroethane as the solvent on a 500 MHz machineand, in selected cases, confirmed by ¹³C NMR. Resconi has reportedproton and carbon assignments (neat perdeuterated tetrachloroethane usedfor proton spectra while a 50:50 mixture of normal and perdeuteratedtetrachloroethane was used for carbon spectra; all spectra were recordedat 100° C. on a Bruker AM 300 spectrometer operating at 300 MHz forproton and 75.43 MHz for carbon) for vinyl terminated propyleneoligomers in J American Chemical Soc., 114, 1992, pp. 1025-1032 that areuseful herein.

“Isobutyl chain end”, also referred to as an “isobutyl end group,” isdefined to be a polyolefin (oligomer or polymer) having at least oneterminus represented by the formula:

where M represents the polyolefin (oligomer or polymer) chain. In apreferred embodiment, the isobutyl chain end is represented by one ofthe following formulae:

where M represents the polyolefin chain.

The percentage of isobutyl end groups is determined using ¹³C NMR (asdescribed in the example section) and the chemical shift assignments inResconi et al., J. Am. Chem. Soc., 1992, 114, pp. 1025-1032 for 100%propylene oligomers (and polymers) and set forth in FIG. 2 of WO2009/155471 for E-P oligomers (and polymers).

The “isobutyl chain end to allylic vinyl group ratio” is defined to bethe ratio of the percentage of isobutyl chain ends to the percentage ofallylic vinyl groups.

Unless otherwise indicated, the term “internal unsaturation” means adouble bond that is not an allyl chain end as defined above, a vinylene,or vinylidene unsaturation.

The term “diblock” is defined to mean that there are two differentsegments in the multiblock polyolefin, e.g., the PO segment and the(CR¹⁷R¹⁸)_(m)—O)_(n) segment in Formula (X) are different, where theterm “different” indicates that the mer units of the segments differfrom each other by at least one atom, the mer units of the segmentsdiffer isomerically, the segments differ in Mn, Mw, Mz, tacticity,Mw/Mn, g′vis, vinyl, vinylidene, vinylene, or internal unsaturationcontent, amount of comonomer (when the comonomer is the same ordifferent in the segments), density (ASTM D 1505), melting point, heatof fusion, Brookfield viscosity, specific gravity (ASTM D 4052), or anyother fluid or polyolefin property described in US 2008/0045638 (inevent of conflict between test procedures in the instant specificationand US 2008/0045638, the instant specification shall control). The term“triblock” means is defined to mean that there are three differentsegments in the functionalized multiblock polyolefin, e.g., two POsegments and the (CR¹⁷R¹⁸)_(m)—O)_(n) segment in Formula (XX) where thePO segment is different from the (CR¹⁷R¹⁸)_(m)—O)_(n) segment and thetwo PO's may be the same or different, where the term “different”indicates that the mer units of the segments differ from each other byat least one atom, the mer units of the segments differ isomerically,the segments differ in Mn, Mw, Mz, tacticity, Mw/Mn, g′vis, vinyl,vinylidene, vinylene, or internal unsaturation content, amount ofcomonomer (when the comonomer is the same or different in the segments),density (ASTM D 1505), melting point, heat of fusion, Brookfieldviscosity, specific gravity (ASTM D 4052), or any other fluid orpolyolefin property described in US 2008/0045638, (in event of conflictbetween test procedures in the instant specification and US2008/0045638, the instant specification shall control). The term“multiblock” is defined to mean at least two segments, a PO segment anda (CR¹⁷R¹⁸)_(m)—O)_(n)) segment are present in the functionalizedmultiblock polyolefin and encompasses the terms “diblock” and“triblock”. The term “vinyl terminated polyolefin” also referred to as“vinyl terminated macromer” or “VTM” is defined to be a polyolefin(oligomer or polymer) having at least 30% allyl chain ends (relative tototal unsaturation), preferably having an Mn of at least 300 g/mol,preferably from 500 to 100,000 g/mol.

As used herein, the new notation for the Periodic Table Groups is usedas described in Chemical and Engineering News, 63(5), pg. 27, (1985).

The term “substituted” means that a hydrogen group has been replacedwith a hydrocarbyl group, a heteroatom or a heteroatom containing group.For example, methyl cyclopentadiene (Cp) is a Cp group substituted witha methyl group and ethyl alcohol is an ethyl group substituted with an—OH group.

The terms “hydrocarbyl radical,” “hydrocarbyl,” and “hydrocarbyl group”are used interchangeably throughout this document. Likewise the terms“group” and “substituent” are also used interchangeably in thisdocument. For purposes of this disclosure, “hydrocarbyl radical” isdefined to be C₁-C₂₀ radicals, that may be linear, branched, or cyclic(aromatic or non-aromatic); and include substituted hydrocarbyl radicalsas defined below.

Substituted hydrocarbyl radicals are radicals in which at least onehydrogen atom has been substituted with a heteroatom or heteroatomcontaining group, preferably with at least one functional group such ashalogen (Cl, Br, I, F), NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*,BR*₂, SiR*₃, GeR*₃, SnR*₃, PbR*₃, and the like or where at least oneheteroatom has been inserted within the hydrocarbyl radical, such ashalogen (Cl, Br, I, F), O, S, Se, Te, NR*, PR*, AsR*, SbR*, BR*, SiR*₂,GeR*₂, SnR*₂, PbR*₂, and the like, where R* is, independently, hydrogenor a hydrocarbyl.

A “substituted alkyl” or “substituted aryl” group is an alkyl or arylradical made of carbon and hydrogen where at least one hydrogen isreplaced by a heteroatom, a heteroatom containing group, or a linear,branched, or cyclic substituted or unsubstituted hydrocarbyl grouphaving 1 to 30 carbon atoms.

By “reactive termini” is meant a polymer having a vinyl, vinylidene,vinylene, or other terminal group that can be polymerized into a growingpolymer chain.

Bromine number is determined by ASTM D 1159.

ICPES (Inductively Coupled Plasma Emission Spectrometry), which isdescribed in J. W. Olesik, “Inductively Coupled Plasma-Optical EmissionSpectroscopy,” in the Encyclopedia of Materials Characterization, C. R.Brundle, C. A. Evans, Jr., and S. Wilson, Eds., Butterworth-Heinemann,Boston, Mass., 1992, pp. 633-644, is used to determine the amount of anelement in a material.

The following abbreviations may be used through this specification: Meis methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl,n-Pr is normal propyl, Bu is butyl, iBu is isobutyl, tBu is tertiarybutyl, p-tBu is para-tertiary butyl, nBu is normal butyl, TMS istrimethylsilyl, TIBAL is triisobutylaluminum, TNOAL is triisobutyln-octylaluminum, MAO is methylalumoxane, pMe is para-methyl, Ar* is2,6-diisopropylaryl, Bz is benzyl, THF is tetrahydrofuran, RT is roomtemperature and tol is toluene.

This invention relates to a process to functionalize vinyl terminatedpolyolefin comprising contacting an alkene metathesis catalyst with anacrylate or methacrylate functionalized polyalkylene glycol, and one ormore vinyl terminated polyolefins, preferably comprising one or more ofthe vinyl terminated polyolefins described herein. This invention alsorelates to the functionalized mutiblock polyolefins produced thereby.

Functionalized Multiblock Polyolefins

In one aspect, a functionalized multiblock polyolefin produced by thisinvention is represented by the formula (X) or (XX):PO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(O)—O—((CR¹⁵R¹⁶)_(z)—(CR¹⁷R¹⁸)_(m)—O)_(n)—R¹⁹  (X)orPO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(O)—O—((CR¹⁵R¹⁶)_(z)—(CR¹⁷R¹⁸)_(m)O)_(n)—C(O)—C(R¹⁴)═C(R¹³)—C(R¹²)(R¹¹)—PO  (XX),wherein R¹¹, R¹², R¹³, and R¹⁴ are each, independently, a substituted orunsubstituted C₁ through C₄ hydrocarbyl group (preferably substituted orunsubstituted methyl, ethyl, propyl, butyl, and isomers thereof) or ahydrogen;R¹⁵, R¹⁶, R¹⁷, and R¹⁸ are each independently a substituted orunsubstituted C₁ through C₄ hydrocarbyl group (preferably substituted orunsubstituted methyl, ethyl, propyl, butyl, and isomers thereof) or ahydrogen;R¹⁹ is a C₁ to a C₂₀ substituted or unsubstituted hydrocarbyl group(preferably substituted or unsubstituted methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl, docecyl, and isomersthereof) or a hydrogen;z is ≧1 to about 5, preferably 2, 3, 4, or 5;m is ≧1 to about 5, preferably 2, 3, 4, or 5;each PO is, independently, a polyolefin hydrocarbyl group comprising 10to 4000 carbon atoms (preferably 15 to 3500, preferably 100 to 2500);andn is from 1 to about 10,000, preferably 2 to 1000, preferably 3 to 500,preferably 4 to 300, preferably 4 to 150, preferably 4 to 50, preferably4 to 20.

In a preferred embodiment, in Formula (X) R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶,R¹⁷, and R¹⁸ are each hydrogen atoms and R¹⁹ is a hydrogen, a methyl oran ethyl group. In preferred embodiment, in Formula (XX) R¹¹, R¹², R¹³,R¹⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ are hydrogen.

In a preferred embodiment, z is 1, m is 1, and n is from 2 to about1000; alternately z is 2, m is 1, and n is from 2 to about 1000;alternately z is 2, m is 2, and n is from 2 to about 1000.

In a preferred embodiment, PO has at least 15 carbon atoms, preferablyat least 100 carbon atoms.

In a preferred embodiment, RH through R¹⁴ are all hydrogens and one ofR¹⁵ through R¹⁸ is a C₁-C₆ hydrocarbon.

In another preferred embodiment, R¹² through R¹⁸ comprise six hydrogensand one C₁-C₆ hydrocarbon.

In another preferred embodiment, R¹² through R¹⁸ comprise six hydrogensand one methyl group.

In a preferred embodiment, the functionalized multiblock polyolefin isamphiphilic, e.g., n is greater than 1, preferably from 1 to 100, and POis a hydrocarbyl or a substituted hydrocarbyl, provided that if PO is asubstituted hydrocarbyl, then PO is not water soluble. Preferably, oneof “(CR¹⁷R¹⁸)_(m)—O)_(n)” or PO in Formula (X) or (XX) is hydrophobicand the other is hydrophilic.

In another embodiment, the two PO groups in Formula (XX) are different.(For convenience, the two different PO groups in Formula (XX) can bereferred to as PO and PO* in the following discussion). An example oftwo different PO groups would be having PO being isotactic PP and PO*being an EP copolymer, with the ethylene content in the PO* being from 5wt % to 60 wt %, preferably about 50 wt %. A preferred embodiment forthe functionalized multiblock polyolefin of Formula (XX) has PO and PO*being different, with PO being immiscible with PO*. By immiscible ismeant that if the vinyl terminated polyolefins that become PO and PO*were blended together they would form a heterogeneous composition.

By homogeneous composition it is meant a composition havingsubstantially one morphological phase. (A co-continuous morphology isconsidered a single state for purposes of this invention and the claimsthereto.) For example, a blend of two polymers where one polymer ismiscible with another polymer is said to be homogeneous in the solidstate. Such morphology is determined using optical microscopy, scanningelectron microscopy (SEM) or atomic force microscopy (AFM), in the eventthe optical microscopy, SEM and AFM provide different data, then the SEMdata shall be used. By contrast, two separate phases would be observedfor an immiscible blend. A miscible blend is homogeneous, while animmiscible blend is heterogeneous.

In a preferred embodiment, PO and PO*, and/or the vinyl terminatedpolyolefins PO and PO* are derived from, differ by at least 5% relativeto each other, preferably by at least 10% different, preferably by atleast 20% different, preferably by at least 30% different, preferably byat least 40%, preferably by at least 50% different, preferably by atleast 60% different, preferably by at least 75%, preferably by at least100% different, preferably by at least 150% different, preferably by atleast 200% in Mn, Mw, Mz, tacticity, Mw/Mn, g′vis, vinyl, vinylidene,vinylene, or internal unsaturation content, amount of comonomer (whenthe comonomer is the same or different in the segments), density (ASTM D1505), melting point, heat of fusion, Brookfield viscosity, specificgravity (ASTM D 4052), or any other fluid or polyolefin propertydescribed in US 2008/0045638 (in event of conflict between testprocedures in the instant specification and US 2008/0045638, the instantspecification shall control). In another embodiment, PO and PO*, and/orthe vinyl terminated polyolefins PO and PO* are derived from, differ by5% to 1000%, relative to each other, preferably by 10% to 200%,preferably by 20% to 100%.

In a preferred embodiment, PO and PO*, and/or the vinyl terminatedpolyolefins PO and PO* are derived from, differ in comonomer contentpreferably by at least 5 mol %, relative to each other, preferably by atleast 10 mol % different, preferably by at least 20 mol % different,preferably by at least 30 mol % different, preferably by at least 40 mol% (for example, an ethylene copolymer having 20 mol % propylene differsfrom a propylene copolymer having 5 mol % butene by 15 mol %). In apreferred embodiment, PO and PO*, and/or the vinyl terminatedpolyolefins PO and PO* are derived from, differ in Mn, Mw, Mz, Mw/Mn,g′vis, vinyl, vinylidene, vinylene, or internal unsaturation content,density (ASTM D-1505), melting point, heat of fusion, % tacticity,and/or crystallization point by at least 5% relative to each other,preferably by at least 10% different, preferably by at least 20%different, preferably by at least 30% different, preferably by at least40% (for example, a polymer having an Mw of 500 g/mol differs from apolymer having an Mw of 732 by 46%). In a preferred embodiment, theTm's, according to the DSC, of PO and PO*, and/or the vinyl terminatedpolyolefins PO and PO* are derived from, are different by at least 5°C., preferably by at least 10° C., preferably by at least 20° C.,preferably by at least 30° C., preferably by at least 40° C., preferablyby at least 50° C., preferably by at least 60° C., preferably by atleast 70° C., preferably by at least 80° C. Likewise, in a preferredembodiment, the crystallization temperatures (Tc), according to the DSC,of PO and PO*, and/or the vinyl terminated polyolefins PO and PO* arederived from, are different by at least 5° C., preferably by at least10° C., preferably by at least 20° C., preferably by at least 30° C.,preferably by at least 40° C., preferably by at least 50° C., preferablyby at least 60° C., preferably by at least 70° C., preferably by atleast 80° C. Further, in a preferred embodiment, the heat of fusion(Hf), determined by DSC, of PO and PO*, and/or the vinyl terminatedpolyolefins PO and PO* are derived from, are at least 5 J/g different,preferably at least 10 J/g different, preferably at least 20 J/gdifferent, preferably at least 50 J/g different, preferably at least 80J/g different.

In a preferred embodiment, the functionalized multiblock polyolefincomposition (i.e., the functionalized multiblock polyolefin and anyunreacted starting materials, prior to fractionation or washing), haslittle or no reactive termini as shown by a ratio of 2.0 or greater(preferably 5 or greater, preferably 10 or greater, preferably 20 orgreater) for the intensity of the internal unsaturation peaks at about128 to 132 ppm to the reactive termini peaks at about 114 and 139 ppm inthe ¹³C NMR spectrum.

In certain embodiments, the functionalized multiblock polymer of Formula(X) has an average of about 0.75 to about 1.25 internal unsaturationsites per polyolefin chain, as determined by ¹H NMR of the polyolefinfor functionalized multiblock polymers having an Mn of up to 60,000g/mol as determined by ¹H NMR.

In certain embodiments, the functionalized multiblock polymer of Formula(XX) has an average of about 1.50 to about 2.50 internal unsaturationsites per polyolefin chain, as determined by ¹H NMR of the polyolefinfor multiblock polymers having an Mn of up to 60,000 g/mol as determinedby ¹H NMR.

In a preferred embodiment, the various components of the functionalizedmultiblock polyolefin can be separated from each other using thepreparative TREF procedure below. In a preferred embodiment, once thefunctionalized multiblock polyolefin has been fractionated, the fractioncontaining the largest mass is selected (and is presumed to be themultiblock polyolefin produced herein) and subjected tocharacterization, such as DSC (as described below). Preferably, themultiblock polyolefin (e.g., the selected fraction with the largestmass) shows at least two peak melting temperatures (Tm) according to theDSC (at least 3 Tm's if PO and PO* are different) and the Tm's are eachdifferent from the other by at least 5° C., preferably by at least 10°C., preferably by at least 20° C., preferably by at least 30° C.,preferably by at least 40° C., preferably by at least 50° C., preferablyby at least 60° C., preferably by at least 70° C., preferably by atleast 80° C. Likewise, preferably the multiblock polyolefin (e.g., theselected fraction with the largest mass) shows at least twocrystallization temperatures (Tc) according to the DSC (at least threeTc's if PO and PO* are different) and the Tc's are each different fromthe other by at least 5° C., preferably by at least 10° C., preferablyby at least 20° C., preferably by at least 30° C., preferably by atleast 40° C., preferably by at least 50° C., preferably by at least 60°C., preferably by at least 70° C., preferably by at least 80° C. Furtherin a preferred embodiment, the heat of fusion (Hf), determined by DSC,of the multiblock polyolefin (e.g., the selected fraction with thelargest mass) is between the Hf's of the starting vinyl terminatedpolyolefins. Preferably, the Hf of the multiblock polyolefin (e.g., theselected fraction with the largest mass) is at least 5 J/g differentthan the Hf of the starting vinyl terminated polyolefin having thehighest Hf, preferably at least 10 J/g different, preferably at least 20J/g different, preferably at least 50 J/g different, preferably at least80 J/g different. In a preferred embodiment, the Hf of the multiblockpolyolefin (e.g., the selected fraction with the largest mass) is atleast 5 J/g less than the Hf of the starting vinyl terminated polyolefinhaving the highest Hf, preferably at least 10 J/g less, preferably atleast 20 J/g less, preferably at least 30 J/g less, preferably at least40 J/g less, preferably at least 50 J/g less, preferably at least 60 J/gless, preferably at least 70 J/g less, preferably at least 80 J/g less,preferably at least 90 J/g less.

In another embodiment, the comonomer content of the multiblockpolyolefin (e.g., the selected fraction with the largest mass) is atleast 5 mol % different than the comonomer content of the starting vinylterminated polyolefin having the highest comonomer content, preferablyat least 10 mol % different, preferably at least 20 mol % different,preferably at least 30 mol % different, preferably at least 40 mol %different. In another embodiment, the comonomer content, of themultiblock polyolefin (e.g., the selected fraction with the largestmass) is between the comonomer contents of the starting vinyl terminatedpolyolefins. A homopolymer shall be considered to have 0 mol %comonomer. Comonomer content can be measured by Fourier TransformInfrared Spectroscopy (FTIR) in conjunction with samples collected byGPC as described in Wheeler and Willis, Applied Spectroscopy, 1993, Vol.47, pp. 1128-1130.

A commercial preparative TREF instrument (Model MC2, Polymer Char S.A.)is used to fractionate the resin into Chemical Composition Fractions.Approximately 2 g of polymer is placed into a reactor and dissolved in200 mL of xylene, stabilized with 600 ppm of BHT, at 130° C. forapproximately 60 minutes. The mixture is allowed to equilibrate for 45minutes at 90° C., and then cooled to either 30° C. (standard procedure)or 15° C. (cryo procedure) using a cooling rate of 0.1° C./min. Thetemperature of the cooled mixture is increased until it is within thelowest Isolation Temperature Range to be used (see Table 2) and themixture is heated to maintain its temperature within the specified rangefor 20 minutes. The mixture is sequentially filtered through a 75 microncolumn filter and then a 2 micron disk filter using 10 psi to 50 psi ofpressurized nitrogen. The reactor is washed twice with 50 ml of xyleneheated to maintain the temperature of the wash mixture within thedesignated temperature range and held at that temperature for 20 minutesduring each wash cycle. The fractionation process is continued byintroducing fresh xylene (200 mL of xylene, stabilized with 600 ppm ofBHT) into the reactor, increasing the temperature of the mixture untilit reaches the next highest Isolation Temperature Range in the sequenceindicated in Table 2 and heating the mixture to maintain its temperaturewithin the specified range for 20 minutes prior to filtering it asdescribed above. The extraction cycle is sequentially repeated in thismanner until the mixture has been extracted at all Isolation TemperatureRanges shown in Table 2. The extracts are independently precipitatedwith methanol to recover the individual polymer fractions.

TABLE 2 Preparative TREF Fractionation Isolation Temperature RangesChemical Composition Isolation Fraction Designation Temperature CryoProcedure Standard Procedure Range (° C.) 1 —  0 to 15 2 1  15 to 36* 32 36 to 51 4 3 51 to 59 5 4 59 to 65 6 5 65 to 71 7 6 71 to 77 8 7 77 to83 9 8 83 to 87 10 9 87 to 91 11 10 Greater than 91 *The IsolationTemperature Range for the Standard Procedure is 0° C. to 36° C.

In a preferred embodiment, the functionalized multiblock polyolefin hasan Mn of from 400 to 120,000 g/mol, preferably from 1000 to about 60,000g/mol, preferably from 10,000 to 45,000 g/mol, preferably from 20,000 to42,000 g/mol, preferably about 40,000 g/mol, alternately about 20,000,alternately about 1000 g/mol.

In an embodiment, PO is a polypropylene of a Mn of about 300 to about20,000 g/mol or PO is an ethylene/propylene copolymer of a Mn of about300 to about 20,000 g/mol. In a preferred embodiment, at least one ofthe substituted or unsubstituted hydrocarbyl groups of PO and PO*contain from about 2 to about 18 carbon atoms.

The character of the “segments” or “blocks” (e.g., the PO, the segmentcontaining “(CR¹⁷R¹⁸)_(m)—O)_(n)” and PO*, if present) of thefunctionalized multiblock polyolefin can be confirmed by the followingsteps: 1. Purifying the multiblock polymer to wash away any unreactedvinyl terminated polymers to other material that is not the multiblockpolyolefin. (The methods to do such will necessarily vary depending onthe nature of the segment containing “(CR¹⁷R¹⁸)_(m)—O)_(n)”, PO, andPO*. Selection of such methods is well within the skill of one ofordinary skill in the art.); 2. Contacting the multiblock polyolefinwith an agent to cause cleavage at the internal unsaturation, such as bycross metathesis with ethylene, or cleavage with ozone or permanganate(care should be taken to not cause cleavage a sites other than theinternal unsaturation. Selection of such agents is well within the skillof one of ordinary skill in the art.); 3. Recovering and separating thecleaved materials. (The methods to do such will necessarily varydepending on the nature of the segment containing“(CR¹⁷R¹⁸)_(m)—O)_(n)”, PO and PO*. Selection of such methods is wellwithin the skill of one of ordinary skill in the art.); and 4.Characterizing the separated materials.

This invention presumes that PO and PO* are derived from the vinylterminated polyolefins used to make the functionalized multiblockpolyolefins.

In another embodiment, the functionalized (and optionally derivatized,as described below) multiblock polyolefins described herein have lessthan 10% allyl chain ends, preferably less than 8%, preferably less than6%, preferably less than 5%, preferably less than 4%, preferably lessthan 3%, preferably less than 2%, preferably less than 1% (relative tototal unsaturations as measured by ¹H NMR, using the protocol describedin WO 2009/155471).

In another embodiment, the functionalized multiblock polyolefinsdescribed herein have less than 10% allyl chain ends, preferably lessthan 5%, preferably less than 1%, (relative to total unsaturations asmeasured by ¹H NMR, using the protocol described in WO 2009/155471); andless than 10% vinylidene unsaturations, preferably less than 5%,preferably less than 1%, (relative to total unsaturations as measured by¹H NMR); and/or less than 10% vinylene unsaturations, preferably lessthan 5%, preferably less than 1%, (relative to total unsaturations asmeasured by ¹H NMR, using the protocol described in WO 2009/155471). Nohydrogen or chain transfer/termination agent should be used duringfunctionalization, derivatization or stripping (of unreacted monomer)for measurement of unsaturations.

In another embodiment, the functionalized multiblock polyolefins consistessentially of propylene, functional group, and optionally ethylene.Alternately C₄ olefins (such as isobutylene, butadiene, n-butene) aresubstantially absent from the functionalized multiblock polyolefins.Alternately C₄₋₂₀ olefins are substantially absent from thefunctionalized multiblock polyolefins. Alternately isobutylene issubstantially absent from the functionalized multiblock polyolefins. Bysubstantially absent is meant that the monomer is present in thepolyolefins at 1 wt % or less, preferably at 0.5 wt % or less,preferably at 0 wt %.

In another embodiment, the number of functional groups is present at0.60 to 1.2, alternately 0.75 to 1.1 functional groups per chain(preferably assuming that Mn has not altered by more than 15% ascompared to the Mn of the polyolefin prior to functionalization andoptional derivatization). Number of functional groups per chain=F/Mn, asdetermined by ¹H NMR as follows: the instrument used is a 400 MHz Varianpulsed Fourier transform NMR spectrometer equipped with a variabletemperature proton detection probe operating at 120° C. The sample isdissolved in 1,1,2,2-tetrachloroethane-d₂ (TCE-d₂) or CDCl₃ andtransferred into a 5 mm glass NMR tube. (The solvent has less than10,000 ppm water and is free of other contaminants that could change thechemical shifts in the NMR spectrum.) Acquisition parameters are pulsewidth=45°, acquisition delay=8 s and number of scans=120. Chemicalshifts are determined relative to the residual TCE-d₁ signal which isset to 5.98 ppm and residual CHCl₃, which is set at 7.24 ppm. VRA is thenormalized integrated signal intensity for the vinyls with shiftsbetween from about 4.9 to 5.1 ppm. VDRA is the normalized integratedsignal intensity for the vinylidene resonances between from about 4.65to 4.85 ppm and the vinylene resonances at from about 5.15 to 5.6 ppm.IA is the normalized integrated signal intensities for the aliphaticregion of interest between from about 0 to 2.1 ppm. The number of vinylgroups/1000 Carbons (VI) is determined from the formula:(VRA*1000)/(IA+VRA+VDRA). Likewise, the number of vinylidene & vinylenegroups/1000 carbons (VE) is determined from the formula:(VDRA*1000)/(IA+VRA+VDRA). VRA, VDRA, and IA are the normalizedintegrated signal intensities in the chemical shift regions definedabove. Mn is calculated assuming one unsaturated end-group per oligomerchain. Mn=(14,000 g/mol)/(VI+VE).

After the polyolefins in question are functionalized, it is necessary todetermine the resonances/chemical shift regions of the functional groupto determine % functionalization. To do so, repeat the above ¹H NMRprocedure on a clean sample of the functionalized multiblock polyolefin(e.g., washed to remove unreacted materials, contaminants, etc.). Referto “The Sadtler Guide to NMR Spectra”, Ed. William Walter Simons,published by the Sadtler Research Laboratories, 1972 for assistance indetermining the shift regions for specific functional groups. The numberof functional groups/1000 C's (F)=(FA*1000)/(FA+IA+VRA+VDRA), whereFA=normalized integrated signal intensities in the chemical shift regionof the functional group, and IA, VRA, VDRA are as defined above.

Percent functionalization of the polyolefin ═(F*100)/(F+VI+VE). Thenumber of vinyl groups/1000 carbons (VI*) and number of vinylidenegroups/1000 carbons (VE*) for the functionalized multiblock polyolefinare determined from the ¹H NMR spectra of the functionalized multiblockpolyolefin in the same manner as VI and VE for the unfunctionalizedmultiblock polyolefin. Preferably, the percent functionalization of thepolyolefin is 75% or more, preferably 80% or more, preferably 90% ormore, preferably 95% or more.

The functionalized multiblock polyolefins produced herein may be used ina broad range of applications, such as compatibilizers, tie-layermodifiers, surfactants, surface modifiers, lubricants, detergents,flocculants, viscosity modifiers, Viscosity Index modifiers,emulsifiers, de-emulsifiers, dispersants, plasticizers, surfactants forsoaps, detergents, fabric softeners, antistatics, oil additives,anti-fogging or wetting additives, adhesion promoters additives forlubricants and/or fuels, and the like.

Derivatization

The functionalized multiblock polyolefins described above (e.g., byFormulae (X) and (XX)) may be further derivatized as described in U.S.Pat. No. 6,022,929. For example, the functional groups will react withelectrophiles to form products with new covalent bonds. Examples ofcarbon-based electrophiles include aldehydes, ketones, anhydrides,cyclic anhydrides, and halocarbons. Examples of silicon-basedelectrophiles include chlorosilanes, fluorosilanes, and bromosilanes.

In a preferred embodiment, the functionalized multiblock polyolefinsdescribed herein have been derivitized: i) by reaction with anelectrophile (such as a carbon or silicon-based electrophile); ii) witha molecule containing any of the following functional groups: ketone,aldehyde, cyclic anhydride, bromide, chloride, iodide, fluoride; or iii)with a molecule containing a chlorosilane, bromosilane, or fluorosilanegroup.

Blends of Functionalized Multiblock polyolefins

In some embodiments, the functionalized (and optionally derivatized)multiblock polyolefins produced by this invention may used alone orblended with other polymers. Typically the functionalized (andoptionally derivatized) multiblock polyolefins are present at 99.9 wt %to 0.1 wt % (typically at from 5 wt % to 99.8 wt %, alternately from 10wt % to 99 wt %) in a blend with one or more other polymers, includingbut not limited to, thermoplastic polymer(s) and/or elastomer(s), basedupon the weight of the blend.

In some embodiments, the functionalized (and optionally derivatized)multiblock polyolefins produced by this invention may be blended with0.1 wt % to 99.9 wt % (typically at from 0.2 wt % to 95 wt %,alternately from 1 wt % to 90 wt %, based upon the weight of the blend)of a one or more other polymers, including but not limited to,thermoplastic polymer(s) and/or elastomer(s), based upon the weight ofthe blend.

By thermoplastic polymer(s) is meant a polymer that can be melted byheat and then cooled with out appreciable change in properties.Thermoplastic polymers typically include, but are not limited to,polyolefins, polyamides, polyesters, polycarbonates, polysulfones,polyacetals, polylactones, acrylonitrile-butadiene-styrene resins,polyphenylene oxide, polyphenylene sulfide, styrene-acrylonitrileresins, styrene maleic anhydride, polyimides, aromatic polyketones, ormixtures of two or more of the above. Preferred polyolefins include, butare not limited to, polymers comprising one or more linear, branched orcyclic C₂ to C₄₀ olefins, preferably polymers comprising propylenecopolymerized with one or more C₃ to C₄₀ olefins, preferably a C₃ to C₂₀alpha olefin, more preferably C₃ to C₁₀ alpha-olefins. More preferredpolyolefins include, but are not limited to, polymers comprisingethylene including but not limited to ethylene copolymerized with a C₃to C₄₀ olefin, preferably a C₃ to C₂₀ alpha olefin, more preferablypropylene and/or butene.

By elastomers is meant all natural and synthetic rubbers, includingthose defined in ASTM D1566. Examples of preferred elastomers include,but are not limited to, ethylene propylene rubber, ethylene propylenediene monomer rubber, styrenic block copolymer rubbers (including SI,SIS, SB, SBS, SIBS, and the like, where S=styrene, I=isobutylene, andB=butadiene), butyl rubber, halobutyl rubber, copolymers of isobutyleneand para-alkylstyrene, halogenated copolymers of isobutylene andpara-alkylstyrene, natural rubber, polyisoprene, copolymers of butadienewith acrylonitrile, polychloroprene, alkyl acrylate rubber, chlorinatedisoprene rubber, acrylonitrile chlorinated isoprene rubber,polybutadiene rubber (both cis and trans).

In another embodiment, the functionalized (and optionally derivatized)multiblock polyolefins produced herein may further be combined with oneor more of polybutene, ethylene vinyl acetate, low density polyethylene(density 0.915 to less than 0.935 g/cm³) linear low densitypolyethylene, ultra low density polyethylene (density 0.86 to less than0.90 g/cm³), very low density polyethylene (density 0.90 to less than0.915 g/cm³), medium density polyethylene (density 0.935 to less than0.945 g/cm³), high density polyethylene (density 0.945 to 0.98 g/cm³),ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylicacid, polymethylmethacrylate or any other polymers polymerizable by ahigh-pressure free radical process, polyvinylchloride, polybutene-1,isotactic polybutene, ABS resins, ethylene-propylene rubber (EPR),vulcanized EPR, EPDM, block copolymer, styrenic block copolymers,polyamides, polycarbonates, PET resins, crosslinked polyethylene,copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromaticmonomers, such as polystyrene, poly-1 esters, polyacetal, polyvinylidinefluoride, polyethylene glycols, and/or polyisobutylene. Preferredpolymers include those available from ExxonMobil Chemical Company inBaytown, Tex. under the tradenames EXCEEDTM and EXACTT™.

Tackifiers may be blended with the functionalized (and optionallyderivatized) multiblock polyolefins produced herein and/or with blendsof the functionalized (and optionally derivatized) multiblockpolyolefins produced by this invention (as described above). Examples ofuseful tackifiers include, but are not limited to, aliphatic hydrocarbonresins, aromatic modified aliphatic hydrocarbon resins, hydrogenatedpolycyclopentadiene resins, polycyclopentadiene resins, gum rosins, gumrosin esters, wood rosins, wood rosin esters, tall oil rosins, tall oilrosin esters, polyterpenes, aromatic modified polyterpenes, terpenephenolics, aromatic modified hydrogenated polycyclopentadiene resins,hydrogenated aliphatic resin, hydrogenated aliphatic aromatic resins,hydrogenated terpenes and modified terpenes, and hydrogenated rosinesters. In some embodiments, the tackifier is hydrogenated. In someembodiments, the tackifier has a softening point (Ring and Ball, asmeasured by ASTM E-28) of 80° C. to 140° C., preferably 100° C. to 130°C. The tackifier, if present, is typically present at about 1 wt % toabout 50 wt %, based upon the weight of the blend, more preferably 10 wt% to 40 wt %, even more preferably 20 wt % to 40 wt %.

In another embodiment, the functionalized (and optionally derivatized)multiblock polyolefins of this invention, and/or blends thereof, furthercomprise typical additives known in the art, such as fillers, cavitatingagents, antioxidants, surfactants, adjuvants, plasticizers, block,antiblock, color masterbatches, pigments, dyes, processing aids, UVstabilizers, neutralizers, lubricants, waxes, and/or nucleating agents.The additives may be present in the typically effective amounts wellknown in the art, such as 0.001 wt % to 10 wt %. Preferred fillers,cavitating agents and/or nucleating agents include titanium dioxide,calcium carbonate, barium sulfate, silica, silicon dioxide, carbonblack, sand, glass beads, mineral aggregates, talc, clay, inorganic ormetallic particles (preferably graphene; graphene oxide, single wallnanotubes and multi wall nanotubes), and the like. Preferredantioxidants include phenolic antioxidants, such as Irganox 1010,Irganox, 1076 both available from Ciba-Geigy. Preferred oils includeparaffinic or naphthenic oils such as Primol 352 or Primol 876 availablefrom ExxonMobil Chemical France, S.A. in Paris, France. More preferredoils include aliphatic naphthenic oils, white oils, or the like.

In a particularly preferred embodiment, the functionalized (andoptionally derivatized) multiblock polyolefins produced herein arecombined with polymers (elastomeric and/or thermoplastic) havinganhydride, acid or isocyanate functional groups under conditions suchthat they react. Reaction may be confirmed by an at least 20%(preferably at least 50%, preferably at least 100%) increase in Mw ascompared to the Mw of the functionalized multiblock polyolefin prior toreaction. Such reaction conditions may be increased heat (for example,above the Tm of the functionalized multiblock polyolefin), increasedshear (such as from a reactive extruder), presence or absence ofsolvent, and the like. Useful polymers having functional groups that canbe reacted with the functionalized multiblock polyolefins producedherein include polyesters, polyvinyl acetates, nylons (polyamides),polybutadiene, nitrile rubber, hydroxylated nitrile rubber,ethylene-acrylic acid copolymers and terpolymers, as well as ionomers.

Process to Produce the Functionalized Multiblock Polyolefins

This invention relates to a process to produce a functionalizedmultiblock polyolefin comprising contacting an alkene metathesiscatalyst with an acrylate or methacrylate functionalized polyalkyleneglycol, and one or more vinyl terminated polyolefins (oligomers orpolymers), preferably comprising one or more of the vinyl terminatedpolyolefins described herein.

The reactants are typically combined in a reaction vessel at atemperature of 20° C. to 200° C. (preferably 50° C. to 160° C.,preferably 60° C. to 140° C.) and a pressure of 0 to 1000 MPa(preferably 0.5 to 500 MPa, preferably 1 to 250 MPa) for a residencetime of 0.5 seconds to 10 hours (preferably 1 second to 5 hours,preferably 1 minute to 1 hour).

Typically, from about 0.4 to about 4.0 (e.g., 0.5 to 2.6), preferablyfrom about 1.0 to about 2.0, and most preferably from about 1.1 to about1.7 moles of the acrylate or methacrylate functionalized polyalkyleneglycol reactant are charged to the reactor per mole of polyolefincharged.

Typically, 0.00001 to 0.1 moles, preferably 0.0001 to 0.02 moles,preferably 0.0005 to 0.01 moles of catalyst are charged to the reactorper mole of polyolefin charged.

The process is typically a solution process, although it may be a bulkor high pressure process. Homogeneous processes are preferred. (Ahomogeneous process is defined to be a process where at least 90 wt % ofthe product is soluble in the reaction media.) A bulk homogeneousprocess is particularly preferred. (A bulk process is defined to be aprocess where reactant concentration in all feeds to the reactor is 70volume % or more.) Alternately no solvent or diluent is present or addedin the reaction medium (except for the small amounts used as the carrierfor the catalyst or other additives, or amounts typically found with thereactants; e.g., propane in propylene).

Suitable diluents/solvents for the process include non-coordinating,inert liquids. Examples include straight and branched-chainhydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes,isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic andalicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof such as canbe found commercially (Isopar™); perhalogenated hydrocarbons, such asperfluorinated C₄₋₁₀ alkanes, chlorobenzene, and aromatic andalkylsubstituted aromatic compounds, such as benzene, toluene,mesitylene, and xylene. In a preferred embodiment, aliphatic hydrocarbonsolvents are used as the solvent, such as isobutane, butane, pentane,isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixturesthereof; cyclic and alicyclic hydrocarbons, such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof. In another embodiment, the solvent is not aromatic, preferablyaromatics are present in the solvent at less than 1 wt %, preferably atless than 0.5 wt %, preferably at 0 wt % based upon the weight of thesolvents. In a preferred embodiment, the feed concentration for theprocess is 60 volume % solvent or less, preferably 40 volume % or less,preferably 20 volume % or less.

The process may be batch, semi-batch, or continuous. As used herein, theterm continuous means a system that operates without interruption orcessation. For example, a continuous process to produce a polymer wouldbe one where the reactants are continually introduced into one or morereactors and polymer product is continually withdrawn.

Useful reaction vessels include reactors (including continuous stirredtank reactors, batch reactors, reactive extruder, pipe, or pump).

In a preferred embodiment, the productivity of the process is at least200 g of functionalized multiblock polyolefin per mmol of catalyst perhour, preferably at least 5000 g/mmol/hour, preferably at least 10,000g/mmol/hr, preferably at least 300,000 g/mmol/hr.

In a preferred embodiment, the yield of the catalyst is at least 50 molsof functionalized multiblock polyolefin per mol of catalyst, preferably100 mols of functionalized multiblock polyolefin per mol of catalyst,preferably 200 mols of functionalized multiblock polyolefin per mol ofcatalyst.

This invention further relates to a process, preferably an in-lineprocess, preferably a continuous process, to produce functionalizedmultiblock polyolefin, comprising introducing monomer and catalystsystem into a reactor, obtaining a reactor effluent containing vinylterminated polyolefin, optionally removing (such as flashing off)solvent, unused monomer and/or other volatiles, obtaining vinylterminated polyolefin (such as those described herein), introducingvinyl terminated polyolefin, alkene metathesis catalyst and acrylate ormethacrylate functionalized polyalkylene glycol (as described herein)into a reaction zone (such as a reactor, an extruder, a pipe, and/or apump), and obtaining functionalized multiblock polyolefin (such as thosedescribed herein).

Alkene Metathesis Catalysts

An alkene metathesis catalyst is a compound that catalyzes the reactionbetween a vinyl terminated polyolefin with an acrylate or methacrylatefunctionalized polyalkylene glycol to produce an ester functionalizedmultiblock polyolefin, typically with the elimination of ethylene.

In a preferred embodiment, the alkene metathesis catalyst is representedby the Formula (I):

where:M is a Group 8 metal, preferably Ru or Os, preferably Ru;X and X¹ are, independently, any anionic ligand, preferably a halogen(preferably Cl), an alkoxide or a triflate, or X and X¹ may be joined toform a dianionic group and may form single ring of up to 30 non-hydrogenatoms or a multinuclear ring system of up to 30 non-hydrogen atoms;L and L¹ are, independently, a neutral two electron donor, preferably aphosphine or a N-heterocyclic carbene, L and L¹ may be joined to form asingle ring of up to 30 non-hydrogen atoms or a multinuclear ring systemof up to 30 non-hydrogen atoms;L and X may be joined to form a multidentate monoanionic group and mayform single ring of up to 30 non-hydrogen atoms or a multinuclear ringsystem of up to 30 non-hydrogen atoms;L¹ and X¹ may be joined to form a multidentate monoanionic group and mayform single ring of up to 30 non-hydrogen atoms or a multinuclear ringsystem of up to 30 non-hydrogen atoms;R and R¹ are, independently, hydrogen or C₁ to C₃₀ substituted orunsubstituted hydrocarbyl (preferably a C₁ to C₃₀ substituted orunsubstituted alkyl or a substituted or unsubstituted C₄ to C₃₀ aryl);R¹ and L¹ or X¹ may be joined to form single ring of up to 30non-hydrogen atoms or a multinuclear ring system of up to 30non-hydrogen atoms; andR and L or X may be joined to form single ring of up to 30 non-hydrogenatoms or a multinuclear ring system of up to 30 non-hydrogen atoms.

Preferred alkoxides include those where the alkyl group is a phenol,substituted phenol (where the phenol may be substituted with up to 1, 2,3, 4, or 5 C₁ to C₁₂ hydrocarbyl groups) or a C₁ to C₁₀ hydrocarbyl,preferably a C₁ to C₁₀ alkyl group, preferably methyl, ethyl, propyl,butyl, or phenyl.

Preferred triflates are represented by the Formula (II):

where R² is hydrogen or a C₁ to C₃₀ hydrocarbyl group, preferably a C₁to C₁₂ alkyl group, preferably methyl, ethyl, propyl, butyl, or phenyl.

Preferred N-heterocyclic carbenes are represented by the Formula (III)or the Formula (IV):

where:each R⁴ is independently a hydrocarbyl group or substituted hydrocarbylgroup having 1 to 40 carbon atoms, preferably methyl, ethyl, propyl,butyl (including isobutyl and n-butyl), pentyl, cyclopentyl, hexyl,cyclohexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl, dodecyl,cyclododecyl, mesityl, adamantyl, phenyl, benzyl, toluoyl, chlorophenyl,phenol, substituted phenol, or CH₂C(CH₃)₃; andeach R⁵ is hydrogen, a halogen, or a C₁ to C₁₂ hydrocarbyl group,preferably hydrogen, bromine, chlorine, methyl, ethyl, propyl, butyl, orphenyl.

In other useful embodiments, one of the N groups bound to the carbene informula (III) or (IV) is replaced with an S, O, or P atom, preferably anS atom.

Other useful N-heterocyclic carbenes include the compounds described inHermann, W. A., Chem. Eur. J., 1996, 2, pp. 772 and 1627; Enders, D. etal., Angew. Chem. Int. Ed., 1995, 34, pg. 1021; Alder R. W., Angew.Chem. Int. Ed., 1996, 35, pg. 1121; and Bertrand, G. et al., Chem. Rev.,2000, 100, pg. 39.

In a preferred embodiment, the alkene metathesis catalyst is one or moreoftricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene][3-phenyl-1H-inden-1-ylidene]ruthenium(II)dichloride,tricyclohexylphosphine[3-phenyl-1H-inden-1-ylidene][1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro-imidazol-2-ylidene]ruthenium(II)dichloride,tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene][(phenylthio)methylene]ruthenium(II)dichloride,bis(tricyclohexylphosphine)-3-phenyl-1H-inden-1-ylideneruthenium(II)dichloride,1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(1-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II)dichloride,and[1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(4-methylphenyl)imino]methyl]-4-nitrophenolyl]-[3-phenyl-1H-inden-1-ylidene]ruthenium(II)chloride.

In another embodiment, the alkene metathesis catalyst is represented inFormula (I) above, where: M is Os or Ru; R¹ is hydrogen; X and X¹ may bedifferent or the same and are any anionic ligand; L and L¹ may bedifferent or the same and are any neutral electron donor; and R may behydrogen, substituted or unsubstituted alkyl, or substituted orunsubstituted aryl. R is preferably hydrogen, C₁-C₂₀ alkyl, or aryl. TheC₁-C₂₀ alkyl may optionally be substituted with one or more aryl,halide, hydroxy, C₁-C₂₀ alkoxy, or C₂-C₂₀ alkoxycarbonyl groups. Thearyl may optionally be substituted with one or more C₁-C₂₀ alkyl, aryl,hydroxyl, C₁-C₅ alkoxy, amino, nitro, or halide groups. L and L¹ arepreferably phosphines of the formula PR^(3′)R^(4′)R^(5′), where R^(3′)is a secondary alkyl or cycloalkyl, and R^(4′) and R^(5′) are aryl,C₁-C₁₀ primary alkyl, secondary alkyl, or cycloalkyl. R^(4′) and R^(5′)may be the same or different. L and L¹ preferably the same and are—P(cyclohexyl)₃, —P(cyclopentyl)₃, or —P(isopropyl)₃. X and X¹ are mostpreferably the same and are chlorine.

In another embodiment of the present invention, the ruthenium and osmiumcarbene compounds have the Formula (V):

where M is Os or Ru, preferably Ru; X, X¹, L, and L¹ are as describedabove; and R⁹ and R¹⁰ may be different or the same and may be hydrogen,substituted or unsubstituted alkyl, or substituted or unsubstitutedaryl. The R⁹ and R¹⁰ groups may optionally include one or more of thefollowing functional groups: alcohol, thiol, ketone, aldehyde, ester,ether, amine, imine, amide, nitro, carboxylic acid, disulfide,carbonate, isocyanate, carbodiimide, carboalkoxy, and halogen groups.Such compounds and their synthesis are described in U.S. Pat. No.6,111,121.

In another embodiment, the alkene metathesis catalyst useful herein maybe any of the catalysts described in U.S. Pat. Nos. 6,111,121;5,312,940; 5,342,909; 7,329,758; 5,831,108; 5,969,170; 6,759,537;6,921,735; and U.S. Patent Application Publication No. 2005-0261451 A1,including but not limited to,benzylidene-bis(tricyclohexylphosphine)dichlororuthenium,benzylidene[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(tricyclohexylphosphine)ruthenium,dichloro(o-isopropoxyphenylmethylene)(tricyclohexylphosphine)ruthenium(II),(1,3-Bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(o-isopropoxyphenylmethylene)ruthenium,1,3-Bis(2-methylphenyl)-2-imidazolidinylidene]dichloro(2-isopropoxyphenylmethylene)ruthenium(II),[1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro[3-(2-pyridinyl)propylidene]ruthenium(II),[1,3-Bis(2-methylphenyl)-2-imidazolidinylidene]dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium(II),[1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl-2-butenylidene)(tricyclohexylphosphine)ruthenium(II), and[1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(benzylidene)bis(3-bromopyridine)ruthenium(II).

In another embodiment, the alkene metathesis catalyst is represented bythe formula:

where:M* is a Group 8 metal, preferably Ru or Os, preferably Ru;X* and X¹* are, independently, any anionic ligand, preferably a halogen(preferably Cl), an alkoxide or an alkyl sulfonate, or X and X¹ may bejoined to form a dianionic group and may form single ring of up to 30non-hydrogen atoms or a multinuclear ring system of up to 30non-hydrogen atoms;L* is N, O, P, or S, preferably N or O;R* is hydrogen or a C₁ to C₃₀ hydrocarbyl or substituted hydrocarbyl,preferably methyl;R¹*, R²*, R³*, R⁴*, R⁵*, R⁶*, R⁷*, and R⁸* are, independently, hydrogenor a C₁ to C₃₀ hydrocarbyl or substituted hydrocarbyl, preferablymethyl, ethyl, propyl or butyl, preferably R¹*, R²*, R³*, and R⁴* aremethyl;each R⁹* and R¹³* are, independently, hydrogen or a C₁ to C₃₀hydrocarbyl or substituted hydrocarbyl, preferably a C₂ to C₆hydrocarbyl, preferably ethyl;R¹⁰, R¹¹*, R¹²* are, independently hydrogen or a C₁ to C₃₀ hydrocarbylor substituted hydrocarbyl, preferably hydrogen or methyl;each G, is, independently, hydrogen, halogen or C₁ to C₃₀ substituted orunsubstituted hydrocarbyl (preferably a C₁ to C₃₀ substituted orunsubstituted alkyl or a substituted or unsubstituted C₄ to C₃₀ aryl);where any two adjacent R groups may form a single ring of up to 8non-hydrogen atoms or a multinuclear ring system of up to 30non-hydrogen atoms.

Preferably, any two adjacent R groups may form a fused ring having from5 to 8 non hydrogen atoms. Preferably the non-hydrogen atoms are Cand/or O. Preferably the adjacent R groups form fused rings of 5 to 6ring atoms, preferably 5 to 6 carbon atoms. By adjacent is meant any twoR groups located next to each other, for example R³* and R⁴* can form aring and/or RU* and R¹²* can form a ring.

In a preferred embodiment, the metathesis catalyst compound comprisesone or more of:2-(2,6-diethylphenyl)-3,5,5,5-tetramethylpyrrolidine[2-(1-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium dichloride;2-(mesityl)-3,3,5,5-tetramethylpyrrolidine[2-(1-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium dichloride;2-(2-isopropyl)-3,3,5,5-tetramethylpyrrolidine[2-(1-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium dichloride;2-(2,6-diethyl-4-fluorophenyl)-3,3,5,5-tetramethylpyrrolidine[2-(1-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium dichloride, or mixtures thereof.

For further information on such alkene metathesis catalysts, please seeU.S. Ser. No. 12/939,054, filed Nov. 3, 2010, claiming priority to andthe benefit of U.S. Ser. No. 61/259,514, filed Nov. 9, 2009.

The above named catalysts are generally available from Sigma-AldrichCorp. (St. Louis, Mo.) or Strem Chemicals, Inc. (Newburyport, Mass.).

Acrylate or Methacrylate Functionalized Polyalkylene Glycols

Acrylate or methacrylate functionalized polyalkylene glycols useful inthe process described herein include those represented by the formula(XII) or (XXII):C(R¹³)(R²⁰)═C(R¹⁴)—C(O)—O—((CR¹⁵R¹⁶)_(z)—(CR¹⁷R¹⁸)_(m)—O)_(n)—R¹⁹  (XII)orC(R¹³)(R²⁰)═C(R¹⁴)—C(O)—O—((CR¹⁵R¹⁶)_(z)—(CR¹⁷R¹⁸)_(m)—(O)_(n)—C(O)—C(R¹⁴)═C(R¹³)(R²⁰)  (XXII)wherein R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ are each, independently, asubstituted or unsubstituted C₁ through C₄ hydrocarbyl group (preferablysubstituted or unsubstituted methyl, ethyl, propyl, butyl, and isomersthereof) or a hydrogen;R¹⁹ is a C₁ to a C₂₀ substituted or unsubstituted hydrocarbyl group(preferably substituted or unsubstituted methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl, docecyl, and isomersthereof) or a hydrogen;R²⁰ is a hydrogen or a C₁ to a C₄ substituted or unsubstitutedhydrocarbyl group (preferably substituted or unsubstituted methyl,ethyl, propyl, butyl, and isomers thereof);z is ≧1 to about 5, preferably 2, 3, 4, or 5;m is ≧1 to about 5, preferably 2, 3, 4, or 5; andn is from 1 to about 10,000, preferably 2 to 1000, preferably 3 to 500,preferably 4 to 300, preferably 4 to 150, preferably 4 to 50, preferably4 to 20.

In a preferred embodiment, of Formula (XII) R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, andR¹⁸ are each hydrogen atoms and R¹⁹ is a hydrogen, a methyl, or an ethylgroup. In a preference embodiment, Formula (XXII) R¹³, R¹⁴, R¹⁵, R¹⁶,R¹⁷, and R¹⁸ are hydrogen and R²⁰ is hydrogen, methyl or ethyl group.

In a preferred embodiment z is l, m is 1, and n is from 2 to about 1000;alternately z is 2, m is 1, and n is from 2 to about 1000; alternately zis 2, m is 2, and n is from 2 to about 1000.

In a preferred embodiment, the acrylate or methacrylate functionalizedpolyalkylene glycols (where the alkyl is a C₁ to C₂₀ alkyl group, suchas methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decylundecyl, dodecyl, and isomers thereof), is an acrylate or methacrylatefunctionalized polyethylene glycols, preferably one or more ofpoly(ethylene glycol)diacrylate, poly(ethylene glycol) methyl etheracrylate, poly(ethylene glycol) methyl acrylate, and the like.

Vinyl Terminated Polyolefins

In another embodiment, this invention can be practiced with any vinylcontaining materials, preferably with vinyl terminated polyolefins(including vinyl terminated polymers, (such as vinyl terminated ethylenehomo- and co-polymers, and vinyl terminated propylene homo- andco-polymers). Many of these materials are known in the art and can befunctionalized using the processes described herein, e.g., contacting analkene metathesis catalyst (as described herein) with a acrylate ormethacrylate functionalized polyalkylene glycol (as described herein)and one or more vinyl containing materials. Vinyl terminated polymersinclude homo- and co-polymers of heteroatom containing monomers, as wellas polymers of olefin monomers only. (The term vinyl terminated polymersincludes vinyl terminated oligomers.) Preferred vinyl terminatedpolyolefins include vinyl terminated isotactic polypropylene (preferablyhaving a melting point of 100° C. or more, preferably 155° C. or more),polyethylene (preferably having a melting point of 100° C. or more,preferably 155° C. or more).

Vinyl terminated polyolefins (olefin oligomers and polymers) useful inthis invention include propylene homo-oligomers, comprising propyleneand less than comonomer, preferably 0 wt % comonomer, wherein theoligomer has:

-   -   i) at least 93% allyl chain ends (preferably at least 95%,        preferably at least 97%, preferably at least 98%);    -   ii) a number average molecular weight (Mn) of about 500 to about        20,000 g/mol, as measured by ¹H NMR (preferably 500 to 15,000,        preferably 700 to 10,000, preferably 800 to 8,000 g/mol,        preferably 900 to 7,000, preferably 1000 to 6,000, preferably        1000 to 5,000);    -   iii) an isobutyl chain end to allylic vinyl group ratio of 0.8:1        to 1.3:1.0; and    -   iv) less than 1400 ppm aluminum, (preferably less than 1200 ppm,        preferably less than 1000 ppm, preferably less than 500 ppm,        preferably less than 100 ppm).

Vinyl terminated olefin oligomers and polymers useful in this inventionalso include propylene co-oligomers having an Mn of 300 to 30,000 g/molas measured by ¹H NMR (preferably 400 to 20,000, preferably 500 to15,000, preferably 600 to 12,000, preferably 800 to 10,000, preferably900 to 8,000, preferably 900 to 7,000 g/mol), comprising 10 to 90 mol %propylene (preferably 15 to 85 mol %, preferably 20 to 80 mol %,preferably 30 to 75 mol %, preferably 50 to 90 mol %) and 10 to 90 mol %(preferably 85 to 15 mol %, preferably 20 to 80 mol %, preferably 25 to70 mol %, preferably 10 to 50 mol %) of one or more alpha-olefincomonomers (preferably ethylene, butene, hexene, or octene, preferablyethylene), wherein the oligomer has at least X % allyl chain ends(relative to total unsaturations), where: 1) X=(−0.94 (mol % ethyleneincorporated)+100 {alternately 1.20(−0.94 (mol % ethyleneincorporated)+100), alternately 1.50(−0.94 (mol % ethyleneincorporated)+100)}), when 10 to 60 mol % ethylene is present in theco-oligomer, and 2) X=45 (alternately 50, alternately 60), when greaterthan 60 mol % and less than 70 mol % ethylene is present in theco-oligomer, and 3) X=(1.83*(mol % ethylene incorporated)−83,{alternately 1.20[1.83*(mol % ethylene incorporated)−83], alternately1.50[1.83*(mol % ethylene incorporated)−83]}), when 70 to 90 mol %ethylene is present in the co-oligomer. Alternately X is 80% or more,preferably 85% or more, preferably 90% or more, preferably 95% or more.In an alternate embodiment, the oligomer has at least 80% isobutyl chainends (based upon the sum of isobutyl and n-propyl saturated chain ends),preferably at least 85% isobutyl chain ends, preferably at least 90%isobutyl chain ends. Alternately, the oligomer has an isobutyl chain endto allylic vinyl group ratio of 0.8:1 to 1.35:1.0, preferably 0.9:1 to1.20:1.0, preferably 0.9:1.0 to 1.1:1.0.

Vinyl terminated olefin oligomers and polymers useful in this inventionalso include propylene oligomers, comprising more than 90 mol %propylene (preferably 95 to 99 mol %, preferably 98 to 99 mol %) andless than 10 mol % ethylene (preferably 1 to 4 mol %, preferably 1 to 2mol %), wherein the oligomer has:

-   -   i) at least 93% allyl chain ends (preferably at least 95%,        preferably at least 97%, preferably at least 98%);    -   ii) a number average molecular weight (Mn) of about 400 to about        30,000 g/mol, as measured by ¹H NMR (preferably 500 to 20,000,        preferably 600 to 15,000, preferably 700 to 10,000, preferably        800 to 9,000, preferably 900 to 8,000, preferably 1000 to        6,000);    -   iii) an isobutyl chain end to allylic vinyl group ratio of 0.8:1        to 1.35:1.0, and    -   iv) less than 1400 ppm aluminum, (preferably less than 1200 ppm,        preferably less than 1000 ppm, preferably less than 500 ppm,        preferably less than 100 ppm).

Vinyl terminated olefin oligomers and polymers useful in this inventionalso include propylene oligomers, comprising: at least 50 (preferably 60to 90, preferably 70 to 90) mol % propylene and from 10 to 50(preferably 10 to 40, preferably 10 to 30) mol % ethylene, wherein theoligomer has:

-   -   i) at least 90% allyl chain ends (preferably at least 91%,        preferably at least 93%, preferably at least 95%, preferably at        least 98%);    -   ii) an Mn of about 150 to about 20,000 g/mol, as measured by ¹H        NMR (preferably 200 to 15,000, preferably 250 to 15,000,        preferably 300 to 10,000, preferably 400 to 9,500, preferably        500 to 9,000, preferably 750 to 9,000); and    -   iii) an isobutyl chain end to allylic vinyl group ratio of 0.8:1        to 1.3:1.0, wherein monomers having four or more carbon atoms        are present at from 0 to 3 mol % (preferably at less than 1 mol        %, preferably less than 0.5 mol %, preferably at 0 mol %).

Vinyl terminated olefin oligomers and polymers useful in this inventionalso include propylene oligomers, comprising:

at least 50 (preferably at least 60, preferably 70 to 99.5, preferably80 to 99, preferably 90 to 98.5) mol % propylene, from 0.1 to 45(alternately at least 35, preferably 0.5 to 30, preferably 1 to 20,preferably 1.5 to 10) mol % ethylene, and from 0.1 to 5 (preferably 0.5to 3, preferably 0.5 to 1) mol % C₄ to C₁₂ olefin (such as butene,hexene, or octene, preferably butene), wherein the oligomer has:

-   -   i) at least 90% allyl chain ends (preferably at least 91%,        preferably at least 93%, preferably at least 95%, preferably at        least 98%);    -   ii) a number average molecular weight (Mn) of about 150 to about        15,000 g/mol, as measured by ¹H NMR (preferably 200 to 12,000,        preferably 250 to 10,000, preferably 300 to 10,000, preferably        400 to 9500, preferably 500 to 9,000, preferably 750 to 9,000);        and    -   iii) an isobutyl chain end to allylic vinyl group ratio of 0.8:1        to 1.35:1.0.

Vinyl terminated olefin oligomers and polymers useful in this inventionalso include propylene oligomers, comprising:

at least 50 (preferably at least 60, preferably 70 to 99.5, preferably80 to 99, preferably 90 to 98.5) mol % propylene, from 0.1 to 45(alternately at least 35, preferably 0.5 to 30, preferably 1 to 20,preferably 1.5 to 10) mol % ethylene, and from 0.1 to 5 (preferably 0.5to 3, preferably 0.5 to 1) mol % diene (such as C₄ to C₁₂ alpha-omegadienes (such as butadiene, hexadiene, octadiene), norbornene, ethylidenenorbornene, vinylnorbornene, norbornadiene, and dicyclopentadiene),wherein the oligomer has:

-   -   i) at least 90% allyl chain ends (preferably at least 91%,        preferably at least 93%, preferably at least 95%, preferably at        least 98%);    -   ii) a number average molecular weight (Mn) of about 150 to about        20,000 g/mol, as measured by ¹H NMR (preferably 200 to 15,000,        preferably 250 to 12,000, preferably 300 to 10,000, preferably        400 to 9,500, preferably 500 to 9,000, preferably 750 to 9,000);        and    -   iii) an isobutyl chain end to allylic vinyl group ratio of 0.7:1        to 1.35:1.0.

In another embodiment, the vinyl terminated polyolefins useful hereinmay be one or more vinyl terminated macromers having an Mn (measured by¹H NMR) of 200 g/mol or more, (preferably 300 to 60,000 g/mol, 400 to50,000 g/mol, preferably 500 to 35,000 g/mol, preferably 300 to 15,000g/mol, preferably 400 to 12,000 g/mol, or preferably 750 to 10,000g/mol); and comprising: (i) from about 20 to 99.9 mol % (preferably fromabout 25 to about 90 mol %, from about 30 to about 85 mol %, from about35 to about 80 mol %, from about 40 to about 75 mol %, or from about 50to about 95 mol %) of at least one C₅ to C₄₀ olefin (preferably C₅ toC₃₀ α-olefins, more preferably C₅-C₂₀ α-olefins, preferably, C₅-C₁₂α-olefins, preferably pentene, hexene, heptene, octene, nonene, decene,undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene,cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene,7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof,and isomers thereof, preferably hexene, heptene, octene, nonene, decene,dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene,1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene,dicyclopentadiene, norbornene, norbornadiene, and their respectivehomologs and derivatives, preferably norbornene, norbornadiene, anddicyclopentadiene); and (ii) from about 0.1 to 80 mol % of propylene(preferably from about 5 to 70 mol %, from about 10 to 65 mol %, fromabout 15 to 55 mol %, from about 25 to 50 mol %, or from about 30 to 80mol %); wherein the vinyl terminated polyolefin has at least 40% allylchain ends (preferably at least 50% allyl chain ends, at least 60% allylchain ends, at least 70% allyl chain ends; at least 80% allyl chainends, at least 90% allyl chain ends; at least 95% allyl chain ends);and, optionally, an isobutyl chain end to allylic chain end ratio ofless than 0.70:1 (preferably less than 0.65:1, less than 0.60:1, lessthan 0.50:1, or less than 0.25:1); and further optionally, an allylchain end to vinylidene chain end (as determined by ¹H NMR) ratio ofmore than 2:1 (preferably more than 2.5:1, more than 3:1, more than 5:1,or more than 10:1), and further optionally, an allyl chain end tovinylene chain end ratio of greater than 10:1 (preferably greater than15:1, or greater than 20:1); and even further optionally preferablysubstantially no isobutyl chain ends (preferably less than 0.1 wt %isobutyl chain ends). For further information on such VTM's please seeconcurrently filed U.S. Ser. No. 13/072,249 filed Mar. 25, 2011 andentitled “Vinyl Terminated Higher Olefin Copolymers and Methods toProduce Thereof.”

In another embodiment, the vinyl terminated polyolefin useful herein maybe one or more vinyl terminated polyolefins having an Mn (measured by ¹HNMR) of 200 g/mol or more (preferably 300 to 60,000 g/mol, 400 to 50,000g/mol, preferably 500 to 35,000 g/mol, preferably 300 to 15,000 g/mol,preferably 400 to 12,000 g/mol, or preferably 750 to 10,000 g/mol) andcomprises: (i) from about 80 to 99.9 mol % (preferably 85 to 99.9 mol %,more preferably 90 to 99.9 mol %) of at least one C₄ olefin (preferably1-butene); and (ii) from about 0.1 to 20 mol % of propylene (preferably0.1 to 15 mol %, more preferably 0.1 to 10 mol %); wherein the VTM hasat least 40% allyl chain ends, preferably at least 50% allyl chain ends,at least 60% allyl chain ends, at least 70% allyl chain ends; or atleast 80% allyl chain ends; and, optionally, an isobutyl chain end toallylic chain end ratio of less than 0.70:1, less than 0.65:1, less than0.60:1, less than 0.50:1, or less than 0.25:1; and further optionally,an allyl chain end to vinylidene chain end ratio of more than 2:1, morethan 2.5:1, more than 3:1, more than 5:1, or more than 10:1; and furtheroptionally, an allyl chain end to vinylene chain end ratio of greaterthan 10:1 (preferably greater than 15:1, or greater than 20:1); and evenfurther optionally, preferably substantially no isobutyl chain ends(preferably less than 0.1 wt % isobutyl chain ends). For furtherinformation on such vinyl terminated polyolefin's please seeconcurrently filed U.S. Ser. No. 13/072,249 filed Mar. 25, 2011 andentitled “Vinyl Terminated Higher Olefin Copolymers and Methods toProduce Thereof.”

In particular embodiments herein, the vinyl terminated polyolefin usefulherein may be a vinyl terminated polyolefin having an Mn of at least 200g/mol, (preferably 200 to 100,000 g/mol, preferably 200 to 75,000 g/mol,preferably 200 to 60,000 g/mol, preferably 300 to 60,000 g/mol, orpreferably 750 to 30,000 g/mol) (measured by ¹H NMR) comprising of oneor more (preferably two or more, three or more, four or more, and thelike) C₄ to C₄₀ (preferably C₄ to C₃₀, C₄ to C₂₀, or C₄ to C₁₂,preferably butene, pentene, hexene, heptene, octene, nonene, decene,undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene,cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene,7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof,and isomers thereof) higher olefin derived units, where the vinylterminated higher olefin polymer comprises substantially no propylenederived units (preferably less than 0.1 wt % propylene); and wherein thehigher olefin polymer has at least 5% (at least 10%, at least 15%, atleast 20%, at least 30%, at least 40%, at least 50%, at least 60%, atleast 70% allyl; at least 80%, at least 90%, or at least 95%) allylchain ends; and optionally, an allyl chain end to vinylidene chain endratio of greater than 2:1 (preferably greater than 2.5:1, greater than3:1, greater than 5:1, or greater than 10:1); and further optionally, anallyl chain end to vinylene chain end ratio of greater than 10:1(preferably greater than 15:1, or greater than 20:1); and even furtheroptionally, preferably substantially no isobutyl chain ends (preferablyless than 0.1 wt % isobutyl chain ends). In some embodiments, thesehigher olefin vinyl terminated polymers may comprise ethylene derivedunits, preferably at least 5 mol % ethylene (preferably at least 15 mol% ethylene, preferably at least 25 mol % ethylene, preferably at least35 mol % ethylene, preferably at least 45 mol % ethylene, preferably atleast 60 mol % ethylene, preferably at least 75 mol % ethylene, orpreferably at least 90 mol % ethylene). For further information on suchvinyl terminated polyolefins please see concurrently filed U.S. Ser. No.13/072,288 filed Mar. 25, 2011 and entitled “Vinyl Terminated HigherOlefin Polymers and Methods to Produce Thereof”

In another embodiment, the vinyl terminated polyolefin useful herein isa branched polyolefin having an Mn of 7,500 to 60,000 g/mol (andoptionally a Tm of greater than 60° C. (preferably greater than 100°C.), and/or, optionally, a ΔHf of greater than 7 J/g (preferably greaterthan 50 J/g)) comprising one or more alpha olefins (preferably ethyleneand or propylene and optionally a C₄ to C₁₀ alpha olefin), said branchedpolyolefin having: (i) 50 mol % or greater allyl chain ends, relative tototal unsaturated chain ends (preferably 60% or more, preferably 70% ormore, preferably 80% or more, preferably 90% or more, preferably 95% ormore); (ii) a g′(vis) of 0.90 or less (preferably 0.85 or less,preferably 0.80 or less); (iii) optionally, an allyl chain end tointernal vinylidene ratio of greater than 5:1 (preferably greater than10:1); and (iv) optionally, an allyl chain end to vinylidene chain endratio of greater than greater than 10:1 (preferably greater than 15:1).

In another embodiment, the vinyl terminated polyolefin useful herein isa branched polyolefin having an Mn of 60,000 g/mol or more (andoptionally a Tm of greater than 60° C. (preferably greater than 100°C.), and/or, optionally, a ΔHf of greater than 7 J/g (preferably greaterthan 50 J/g)) comprising one or more alpha olefins (preferably ethyleneand/or propylene and optionally a C₄ to C₁₀ alpha olefin), and having:(i) 50 mol % or greater allyl chain ends, relative to total unsaturatedchain ends (preferably 60% or more, preferably 70% or more, preferably80% or more, preferably 90% or more, preferably 95% or more); (ii) ag′(vis) of 0.90 or less (preferably 0.85 or less, preferably 0.80 orless); (iii) a bromine number which, upon complete hydrogenation,decreases by at least 50% (preferably at least 75%); (iv) optionally, anallyl chain end to internal vinylidene ratio of greater than 5:1(preferably greater than 10:1); and (v) optionally, an allyl chain endto vinylidene chain end ratio of greater than 10:1 preferably greaterthan 15:1).

In another embodiment, the vinyl terminated polyolefin useful herein isa branched polyolefin having an Mn of less than 7,500 g/mol, preferablyfrom 100 to 7,000 g/mol, preferably form 400 to 6,500 g/mol (andoptionally a Tm of greater than 60° C. (preferably greater than 100°C.), and/or, optionally, a ΔHf of greater than 7 J/g (preferably greaterthan 50 J/g)) comprising one or more alpha olefins (preferably ethyleneand or propylene and optionally a C₄ to C₁₀ alpha olefin), and having:(i) 50 mol % or greater allyl chain ends, relative to total unsaturatedchain ends (preferably 60% or more, preferably 70% or more, preferably80% or more, preferably 90% or more, preferably 95% or more); (ii) aratio of percentage of saturated chain ends to percentage of allyl chainends of 1.2 to 2.0 (preferably isobutyl chain ends) to percentage ofallyl chain ends of 1.6 to 1.8, wherein the percentage of saturatedchain ends is determined using ¹³C NMR as described in WO 2009/155471 atparagraph [0095] and [0096] except that the spectra are referenced tothe chemical shift of the solvent, tetrachloroethane-d₂, and/or a ratioof Mn(GPC)/Mn(¹H NMR) of 0.95 or less (preferably 0.90 or less,preferably 0.85 or less, preferably 0.80 or less); and (iii) optionally,a bromine number which, upon complete hydrogenation, decreases by atleast 50% (preferably by at least 75%); (iv) optionally, an allyl chainend to internal vinylidene ratio of greater than 5:1 (preferably greaterthan 10:1); and (v) optionally, an allyl chain end to vinylidene chainend ratio of greater than 2:1 (preferably greater than 10:1), preferablythe branched vinyl terminated polyolefin has a ratio of Mn(GPC)/Mn(¹HNMR) of 0.95 or less (preferably 0.90 or less, preferably 0.85 or less,preferably 0.80 or less).

C₄ to C₁₀ alpha olefin monomers useful in the branched polymersdescribed above include butene, pentene, hexene, heptene, octene,nonene, decene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene,and isomers thereof.

For more information on useful branched polymers and methods to producethem, please see concurrently filed U.S. Ser. No. 61/467,681 filed Mar.25, 2011, and entitled “Branched Vinyl Terminated Polymers and Methodsfor Production Thereof”.

Any of the vinyl terminated polyolefins described herein preferably haveless than 1400 ppm aluminum, preferably less than 1000 ppm aluminum,preferably less than 500 ppm aluminum, preferably less than 100 ppmaluminum, preferably less than 50 ppm aluminum, preferably less than 20ppm aluminum, preferably less than 5 ppm aluminum.

In a preferred embodiment, the vinyl terminated polyolefin used hereincomprises at least 10 mol % (alternately at least 20 mol %, alternatelyat least 40 mol %, alternately at least 60 mol %) of a C₄ or greaterolefin (such as butene, pentene, octene, nonene, decene, undecene,dodecene) and has: 1) at least 30% allyl chain ends (relative to totalunsaturations), preferably at least 40%, preferably at least 50%,preferably at least 60%, preferably at least 70%, preferably at least75%, preferably at least 80%, preferably at least 85%, preferably atleast 90%, preferably at least 95% allyl chain ends (relative to totalunsaturations); and 2) an Mn of from 200 to 60,000 g/mol, preferablyfrom 200 to 50,000 g/mol, preferably from 500 to 40,000 g/mol.

In a preferred embodiment, the vinyl terminated polyolefin comprisesless than 3 wt % of functional groups selected from hydroxide, aryls andsubstituted aryls, halogens, alkoxys, carboxylates, esters, acrylates,oxygen, nitrogen, and carboxyl, preferably less than 2 wt %, morepreferably less than 1 wt %, more preferably less than 0.5 wt %, morepreferably less than 0.1 wt %, more preferably 0 wt %, based upon theweight of the oligomer.

The vinyl terminated polyolefin preferably has an M_(n) as determined by¹H NMR of 150 to 25,000 g/mol, 200 to 20,000 g/mol, preferably 250 to15,000 g/mol, preferably 300 to 15,000 g/mol, preferably 400 to 12,000g/mol, preferably 750 to 10,000 g/mol. Further, a desirable molecularweight range can be any combination of any upper molecular weight limitwith any lower molecular weight limit described above. M_(n) isdetermined according to the methods described below in the examplessection.

The vinyl terminated polyolefin preferably has a glass transitiontemperature (Tg) of less than 0° C. or less (as determined bydifferential scanning calorimetry as described below), preferably −10°C. or less, more preferably −20° C. or less, more preferably −30° C. orless, more preferably −50° C. or less.

The vinyl terminated polyolefin preferably contains less than 80 wt % ofC₄ olefin(s), (such as isobutylene n-butene, 2-butene, isobutylene, andbutadiene), based upon the weight of the vinyl terminated polyolefin,preferably less than 10 wt %, preferably 5 wt %, preferably less than 4wt %, preferably less than 3 wt %, preferably less than 2 wt %,preferably less than 1 wt %, preferably less than 0.5 wt %, preferablyless than 0.25 wt % of C₄ olefins) based upon the weight of the vinylterminated polyolefin.

Alternately, the vinyl terminated polyolefin preferably contains lessthan 20 wt % of C₄ or more olefin(s), (such as C₄ to C₃₀ olefins,typically such as C₄ to C₁₂ olefins, typically such as C₄, C₆, C₈, C₁₂,olefins, etc.), based upon the weight of the vinyl terminatedpolyolefin, preferably less than 10 wt %, preferably 5 wt %, preferablyless than 4 wt %, preferably less than 3 wt %, preferably less than 2 wt%, preferably less than 1 wt %, preferably less than 0.5 wt %,preferably less than 0.25 wt % of C₄ olefin(s) based upon the weight ofthe vinyl terminated polyolefin, as determined by ¹³C NMR.

In another embodiment, the vinyl terminated polyolefin compositionproduced comprises at least 50 wt % (preferably at least 75 wt %,preferably at least 90 wt %, based upon the weight of the oligomercomposition) olefins having at least 36 carbon atoms (preferably atleast 51 carbon atoms, preferably at least 102 carbon atoms) as measuredby ¹H NMR assuming one unsaturation per chain.

In another embodiment, the vinyl terminated polyolefin compositionproduced comprises less than 20 wt % dimer and trimer (preferably lessthan 10 wt %, preferably less than 5 wt %, more preferably less than 2wt %, based upon the weight of the oligomer composition), as measured bygas chromotography. Products are analyzed by gas chromatography (Agilent6890N with auto-injector) using helium as a carrier gas at 38 cm/sec. Acolumn having a length of 60 m (J & W Scientific DB-1, 60 m×0.25 mmI.D.×1.0 μm film thickness) packed with a flame ionization detector(FID), an Injector temperature of 250° C., and a Detector temperature of250° C. are used. The sample was injected into the column in an oven at70° C., then heated to 275° C. over 22 minutes (ramp rate 10° C./min to100° C., 30° C./min to 275° C., hold). An internal standard, usually themonomer, is used to derive the amount of dimer or trimer product that isobtained. Yields of dimer and trimer product are calculated from thedata recorded on the spectrometer. The amount of dimer or trimer productis calculated from the area under the relevant peak on the GC trace,relative to the internal standard.

Particularly useful vinyl terminated polyolefins may be isotactic,highly isotactic, syndiotactic, or highly syndiotactic propylenepolymer, particularly isotactic polypropylene. As used herein,“isotactic” is defined as having at least 10% isotactic pentads,preferably having at least 40% isotactic pentads of methyl groupsderived from propylene according to analysis by ¹³C NMR. As used herein,“highly isotactic” is defined as having at least 60% isotactic pentadsaccording to analysis by ¹³C NMR. In a desirable embodiment, the vinylterminated polyolefin has at least 85% isotacticity. As used herein,“syndiotactic” is defined as having at least 10% syndiotactic pentads,preferably at least 40%, according to analysis by ¹³C NMR. As usedherein, “highly syndiotactic” is defined as having at least 60%syndiotactic pentads according to analysis by ¹³C NMR. In anotherembodiment, the vinyl terminated polyolefin has at least 85%syndiotacticity.

In another embodiment, the vinyl terminated polyolefin produced herecontains less than 25 ppm hafnium, preferably less than 10 ppm hafnium,preferably less than 5 ppm hafnium based on the yield of polymerproduced and the mass of catalyst employed.

In another embodiment, the vinyl terminated polyolefins described hereinmay have a melting point (DSC first melt) of from 60° C. to 130° C.,alternately 50° C. to 100° C. In another embodiment, the vinylterminated polyolefins described herein have no detectable melting pointby DSC following storage at ambient temperature (23° C.) for at least 48hours.

Melting temperature (T_(m)) and glass transition temperature (Tg) aremeasured using Differential Scanning calorimetry (DSC) usingcommercially available equipment such as a TA Instruments 2920 DSC.Typically, 6 to 10 mg of the sample, that has been stored at roomtemperature for at least 48 hours, is sealed in an aluminum pan andloaded into the instrument at room temperature. The sample isequilibrated at 25° C., then it is cooled at a cooling rate of 10°C./min to −80° C. The sample is held at −80° C. for 5 min and thenheated at a heating rate of 10° C./min to 25° C. The glass transitiontemperature is measured from the heating cycle. Alternatively, thesample is equilibrated at 25° C., then heated at a heating rate of 10°C./min to 150° C. The endothermic melting transition, if present, isanalyzed for onset of transition and peak temperature. The meltingtemperatures reported are the peak melting temperatures from the firstheat unless otherwise specified. For samples displaying multiple peaks,the melting point (or melting temperature) is defined to be the peakmelting temperature (i.e., associated with the largest endothermiccalorimetric response in that range of temperatures) from the DSCmelting trace.

In another embodiment, the vinyl terminated polyolefins described hereinare a liquid at 25° C.

In another embodiment, the vinyl terminated polymers (and or thefunctionalized multiblock polyolefins) described herein have a viscosityat 60° C. of greater than 1000 cP, greater than 12,000 cP, or greaterthan 100,000 cP. In other embodiments, the vinyl terminated polymershave a viscosity of less than 200,000 cP, less than 150,000 cP, or lessthan 100,000 cP. Viscosity is measured using a Brookfield DigitalViscometer.

In another embodiment, the vinyl terminated polyolefins described hereinhave an Mw (measured as described below) of 1,000 to about 30,000 g/mol,alternately 2000 to 25,000 g/mol, alternately 3,000 to 20,000 g/moland/or an Mz of about 1700 to about 150,000 g/mol, alternately 800 to100,000 g/mol.

Mw, Mn, Mz, number of carbon atoms, and g′_(vis) are determined by usinga High Temperature Size Exclusion Chromatograph (either from WatersCorporation or Polymer Laboratories), equipped with three in-linedetectors, a differential refractive index detector (DRI), a lightscattering (LS) detector, and a viscometer. Experimental details,including detector calibration, are described in: T. Sun, P. Brant, R.R. Chance, and W. W. Graessley, Macromolecules, Vol. 34, No. 19, pp.6812-6820, (2001) and references therein. Three Polymer LaboratoriesPLgel 10 mm Mixed-B LS columns are used. The nominal flow rate is 0.5cm³/min, and the nominal injection volume is 300 μL. The varioustransfer lines, columns and differential refractometer (the DRIdetector) are contained in an oven maintained at 145° C. Solvent for theexperiment is prepared by dissolving 6 grams of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade 1, 2, 4trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.7μm glass pre-filter and subsequently through a 0.1 μm Teflon filter. TheTCB is then degassed with an online degasser before entering the SizeExclusion Chromatograph. Polymer solutions are prepared by placing drypolymer in a glass container, adding the desired amount of TCB, thenheating the mixture at 160° C. with continuous agitation for about 2hours. All quantities are measured gravimetrically. The TCB densitiesused to express the polymer concentration in mass/volume units are 1.463g/ml at room temperature and 1.324 g/ml at 145° C. The injectionconcentration is from 0.75 to 2.0 mg/ml, with lower concentrations beingused for higher molecular weight samples. Prior to running each samplethe DRI detector and the injector are purged. Flow rate in the apparatusis then increased to 0.5 ml/minute, and the DRI is allowed to stabilizefor 8 to 9 hours before injecting the first sample. The LS laser isturned on 1 to 1.5 hours before running the samples. The concentration,c, at each point in the chromatogram is calculated from thebaseline-subtracted DRI signal, I_(DRI), using the following equation:c=K _(DRI) I _(DRI)/(dn/dc)where K_(DRI) is a constant determined by calibrating the DRI, and(dn/dc) is the refractive index increment for the system. The refractiveindex, n=1.500 for TCB at 145° C. and λ=690 nm. For purposes of thisinvention and the claims thereto (dn/dc)=0.104 for propylene polymers,0.098 for butene polymers and 0.1 otherwise. Units on parametersthroughout this description of the SEC method are such thatconcentration is expressed in g/cm³, molecular weight is expressed ing/mol, and intrinsic viscosity is expressed in dL/g.

The LS detector is a Wyatt Technology High Temperature mini-DAWN. Themolecular weight, M, at each point in the chromatogram is determined byanalyzing the LS output using the Zimm model for static light scattering(M. B. Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press,1971):

$\frac{K_{o}c}{\Delta\;{R(\theta)}} = {\frac{1}{{MP}(\theta)} + {2A_{2}c}}$

Here, ΔR(θ) is the measured excess Rayleigh scattering intensity atscattering angle θ, c is the polymer concentration determined from theDRI analysis, A₂ is the second virial coefficient for purposes of thisinvention, A₂=0.0006 for propylene polymers, 0.0015 for butene polymersand 0.001 otherwise, (dn/dc)=0.104 for propylene polymers, 0.098 forbutene polymers and 0.1 otherwise, P(θ) is the form factor for amonodisperse random coil, and K_(o) is the optical constant for thesystem:

$K_{o} = \frac{4\pi^{2}{n^{2}\left( {{\mathbb{d}n}/{\mathbb{d}c}} \right)}^{2}}{\lambda^{4}N_{A}}$where N_(A) is Avogadro's number, and (dn/dc) is the refractive indexincrement for the system. The refractive index, n=1.500 for TCB at 145°C. and λ=690 nm.

A high temperature Viscotek Corporation viscometer, which has fourcapillaries arranged in a Wheatstone bridge configuration with twopressure transducers, is used to determine specific viscosity. Onetransducer measures the total pressure drop across the detector, and theother, positioned between the two sides of the bridge, measures adifferential pressure. The specific viscosity, η_(s), for the solutionflowing through the viscometer is calculated from their outputs. Theintrinsic viscosity, [η], at each point in the chromatogram iscalculated from the following equation:η_(s) =c[η]+0.3(c[η])²where c is concentration and was determined from the DRI output.

The branching index (g′_(vis)) is calculated using the output of theSEC-DRI-LS-VIS method as follows. The average intrinsic viscosity,[η]_(avg), of the sample is calculated by:

$\lbrack\eta\rbrack_{avg} = \frac{\sum{c_{i}\lbrack\eta\rbrack}_{i}}{\sum c_{i}}$where the summations are over the chromatographic slices, i, between theintegration limits.

The branching index g′_(vis) is defined as:

${g^{\prime}{vis}} = \frac{\lbrack\eta\rbrack_{avg}}{{kM}_{v}^{\alpha}}$where, for purpose of this invention and claims thereto, α=0.695 andk=0.000579 for linear ethylene polymers, α=0.705 k=0.000262 for linearpropylene polymers, and α=0.695 and k=0.000181 for linear butenepolymers. M_(V) is the viscosity-average molecular weight based onmolecular weights determined by LS analysis. See Macromolecules, 2001,34, pp. 6812-6820 and Macromolecules, 2005, 38, pp. 7181-7183, forguidance on selecting a linear standard having similar molecular weightand comonomer content, and determining k coefficients and α exponents.

Molecular weight distribution (Mw/Mn—both by GPC-DRI) is determined bythe method above. In some embodiments, the vinyl terminated polyolefinsof this invention have an Mw/Mn (by GPC-DRI) of 1.5 to 20, alternately1.7 to 10.

In another embodiment, any of the vinyl terminated polyolefins describedor useful herein have 3-alkyl vinyl end groups (where the alkyl is a C₁to C₃₈ alkyl), also referred to as a “3-alkyl chain ends” or a “3-alkylvinyl termination”, represented by the formula:

where “••••” represents the polyolefin chain and R^(b) is a C₁ to C₃₈alkyl group, preferably a C₁ to C₂₀ alkyl group, such as methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,docecyl, and the like. The amount of 3-alkyl chain ends is determinedusing ¹³C NMR as set out below.

In a preferred embodiment, any of the vinyl terminated polyolefinsdescribed or useful herein have at least 5% 3-alkyl chain ends(preferably at least 10% 3-alkyl chain ends, at least 20% 3-alkyl chainends, at least 30% 3-alkyl chain ends; at least 40% 3-alkyl chain ends,at least 50% 3-alkyl chain ends, at least 60% 3-alkyl chain ends, atleast 70% 3-alkyl chain ends; at least 80% 3-alkyl chain ends, at least90% 3-alkyl chain ends; at least 95% 3-alkyl chain ends, relative tototal unsaturation.

In a preferred embodiment, any of the vinyl terminated polyolefinsdescribed or useful herein have at least 5% of 3-alkyl+allyl chain ends,(e.g., all 3-alkyl chain ends plus all allyl chain ends), preferably atleast 10% 3-alkyl+allyl chain ends, at least 20% 3-alkyl+allyl chainends, at least 30% 3-alkyl+allyl chain ends; at least 40% 3-alkyl+allylchain ends, at least 50% 3-alkyl+allyl chain ends, at least 60%3-alkyl+allyl chain ends, at least 70% 3-alkyl+allyl chain ends; atleast 80% 3-alkyl+allyl chain ends, at least 90% 3-alkyl+allyl chainends; at least 95% 3-alkyl+allyl chain ends, relative to totalunsaturation.

Process to Make Vinyl Terminated Oligomers

The vinyl terminated polyolefins described above are typically preparedin a homogeneous process, preferably a bulk process as described in WO2009/155471, which is incorporated by reference herein. In a preferredembodiment, propylene and optional comonomers (such as ethylene) can bepolymerized by reacting a catalyst system (comprising metallocenecompound(s) and one or more activators) with the olefins. Otheradditives may also be used, as desired, such as scavengers and/orhydrogen. Any conventional suspension, homogeneous bulk, solution,slurry, or high-pressure oligomerization process can be used. Suchprocesses can be run in a batch, semi-batch, or continuous mode. Suchprocesses and modes are well known in the art. Homogeneouspolymerization processes are preferred. (A homogeneous polymerizationprocess is defined to be a process where at least 90 wt % of the productis soluble in the reaction media.) A bulk homogeneous process isparticularly preferred. (A bulk process is defined to be a process wheremonomer concentration in all feeds to the reactor is 70 volume % ormore.) Alternately no solvent or diluent is present or added in thereaction medium, (except for the small amounts used as the carrier forthe catalyst system or other additives, or amounts typically found withthe monomer; e.g., propane in propylene). In another embodiment, theprocess is a slurry process. As used herein the term “slurrypolymerization process” means a polymerization process where a supportedcatalyst is employed and monomers are polymerized on the supportedcatalyst particles. At least 95 wt % of polymer products derived fromthe supported catalyst are in granular form as solid particles (notdissolved in the diluent).

Preferred monomers useful herein include one or more of C₁ to C₄₀alkyls, preferably C₁ to C₄₀ (preferably C₁ to C₃₀, C₁ to C₂₀, or C₂ toC₁₂, preferably ethylene, propylene, butene, pentene, hexene, heptene,octene, nonene, decene, undecene, dodecene, norbornene, cyclopentene,cycloheptene, cyclooctene, cyclooctadiene, cyclododecene,7-oxanorbornene, substituted derivatives thereof, and isomers thereof).

In some embodiments, where butene is the comonomer, the butene sourcemay be a mixed butene stream comprising various isomers of butene. The1-butene monomers are expected to be preferentially consumed by thepolymerization process. Use of such mixed butene streams will provide aneconomic benefit, as these mixed streams are often waste streams fromrefining processes, for example C₄ raffinate streams, and can thereforebe substantially less expensive than pure 1-butene.

Suitable diluents/solvents for polymerization include non-coordinating,inert liquids. Examples include straight and branched-chain hydrocarbonssuch as isobutane, butane, pentane, isopentane, hexanes, isohexane,heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclichydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, and mixtures thereof such as can be foundcommercially (Isopars); perhalogenated hydrocarbons, such asperfluorinated C₄₋₁₀ alkanes, chlorobenzene, and aromatic andalkylsubstituted aromatic compounds, such as benzene, toluene,mesitylene, and xylene. Suitable solvents also include liquid olefinswhich may act as monomers or comonomers including ethylene, propylene,1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,1-octene, and 1-decene. Mixtures of the foregoing are also suitable. Ina preferred embodiment, aliphatic hydrocarbon solvents are used as thesolvent, such as isobutane, butane, pentane, isopentane, hexanes,isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic andalicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof. In anotherembodiment, the solvent is not aromatic, preferably aromatics arepresent in the solvent at less than 1 wt %, preferably at less than 0.5wt %, preferably at 0 wt % based upon the weight of the solvents.

In a preferred embodiment, the feed concentration for the polymerizationis 60 volume % solvent or less, preferably 40 volume % or less,preferably 20 volume % or less. Preferably the polymerization is run ina bulk process.

Suitable additives to the polymerization process can include one or morescavengers, promoters, modifiers, reducing agents, oxidizing agents,hydrogen, aluminum alkyls, or silanes.

In a preferred embodiment, hydrogen is present in the polymerizationreactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa),preferably from 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1to 10 psig (0.7 to 70 kPa). It has been found that in the presentsystems, hydrogen can be used to provide increased activity withoutsignificantly impairing the catalyst's ability to produce allylic chainends. Preferably the catalyst activity (calculated as g/mmolcatalyst/hr) is at least 20% higher than the same reaction withouthydrogen present, preferably at least 50% higher, preferably at least100% higher.

“Catalyst productivity” is a measure of how many grams of polymer (P)are produced using a polymerization catalyst comprising W g of catalyst(cat), over a period of time of T hours; and may be expressed by thefollowing formula: P/(T×W) and expressed in units of gPgcat⁻¹ hr⁻¹.Conversion is the amount of monomer that is converted to polymerproduct, and is reported as mol % and is calculated based on the polymeryield and the amount of monomer fed into the reactor. Catalyst activityis a measure of how active the catalyst is and is reported as the massof product polymer (P) produced per mole of catalyst (cat) used(kgP/molcat).

In an alternate embodiment, the productivity at least 4500 g/mmol/hour,preferably 5000 or more g/mmol/hour, preferably 10,000 or moreg/mmol/hr, preferably 50,000 or more g/mmol/hr. In an alternateembodiment, the productivity is at least 80,000 g/mmol/hr, preferably atleast 150,000 g/mmol/hr, preferably at least 200,000 g/mmol/hr,preferably at least 250,000 g/mmol/hr, preferably at least 300,000g/mmol/hr.

In an alternate embodiment, the activity of catalyst compound is atleast 100 g/mmol/hour, preferably 1000 or more g/mmol/hour, preferably5000 or more g/mmol/hr, preferably 10,000 or more g/mmol/hr. In analternate embodiment, the conversion of olefin monomer is at least 10%,based upon the weight of the monomer entering the reaction zone,preferably 40% or more, preferably 60% or more, preferably 80% or more.

Preferred polymerizations can be run at typical temperatures and/orpressures, such as from 25° C. to 150° C., preferably 40° C. to 120° C.,preferably 45° C. to 80° C., and preferably from 0.35 to 10 MPa,preferably from 0.45 to 6 MPa, preferably from 0.5 to 4 MPa.

In a typical polymerization, the residence time of the reaction is up to60 minutes, preferably between 5 to 50 minutes, preferably 10 to 40minutes.

In a preferred embodiment, little or no alumoxane is used in the processto produce the vinyl terminated polyolefins. Preferably, alumoxane ispresent at zero mol %, alternately the alumoxane is present at a molarratio of aluminum to transition metal less than 500:1, preferably lessthan 300:1, preferably less than 100:1, preferably less than 1:1.

In an alternate embodiment, if an alumoxane is used to produce the vinylterminated polyolefins then, the alumoxane has been treated to removefree alkyl aluminum compounds, particularly trimethyl aluminum.

Further, in a preferred embodiment, the activator used herein to producethe vinyl terminated polyolefin is bulky as defined herein and isdiscrete.

In a preferred embodiment, little or no scavenger (such as trialkylaluminum) is used in the process to produce the vinyl terminatedpolyolefins. Preferably, scavenger is present at zero mol %, alternatelythe scavenger is present at a molar ratio of scavenger metal totransition metal of less than 100:1, preferably less than 50:1,preferably less than 15:1, preferably less than 10:1.

In a preferred embodiment, the polymerization: 1) is conducted attemperatures of 0° C. to 300° C. (preferably 25° C. to 150° C.,preferably 40° C. to 120° C., preferably 45° C. to 80° C.); and 2) isconducted at a pressure of atmospheric pressure to 10 MPa (preferably0.35 to 10 MPa, preferably from 0.45 to 6 MPa, preferably from 0.5 to 4MPa); 3) is conducted in an aliphatic hydrocarbon solvent (such asisobutane, butane, pentane, isopentane, hexanes, isohexane, heptane,octane, dodecane, and mixtures thereof; cyclic and alicyclichydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, and mixtures thereof; preferably where aromatics arepresent in the solvent at less than 1 wt %, preferably at less than 0.5wt %, preferably at 0 wt % based upon the weight of the solvents); 4)wherein the catalyst system used in the polymerization comprises lessthan 0.5 mol %, preferably O mol % alumoxane, alternately the alumoxaneis present at a molar ratio of aluminum to transition metal less than500:1, preferably less than 300:1, preferably less than 100:1,preferably less than 1:1); 5) the polymerization occurs in one reactionzone; 6) the productivity of the catalyst compound is at least 80,000g/mmol/hr (preferably at least 150,000 g/mmol/hr, preferably at least200,000 g/mmol/hr, preferably at least 250,000 g/mmol/hr, preferably atleast 300,000 g/mmol/hr); 7) optionally scavengers (such as trialkylaluminum compounds) are absent (e.g., present at zero mol %, alternatelythe scavenger is present at a molar ratio of scavenger metal totransition metal of less than 100:1, preferably less than 50:1,preferably less than 15:1, preferably less than 10:1); and 8)optionally, hydrogen is present in the polymerization reactor at apartial pressure of 0.001 to 50 psig (0.007 to 345 kPa) (preferably from0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1 to 10 psig (0.7to 70 kPa)). In preferred embodiment, the catalyst system used in thepolymerization comprises no more than one catalyst compound. A “reactionzone” also referred to as a “polymerization zone” is a vessel wherepolymerization takes place, for example a batch reactor. When multiplereactors are used in either series or parallel configuration, eachreactor is considered as a separate polymerization zone. For amulti-stage polymerization in both a batch reactor and a continuousreactor, each polymerization stage is considered as a separatepolymerization zone. In a preferred embodiment, the polymerizationoccurs in one reaction zone. Room temperature is 23° C. unless otherwisenoted.

Catalyst Compound to Make Vinyl Terminated Oligomers

A “catalyst system” is combination of at least one catalyst compound, atleast one activator, an optional co-activator, and an optional supportmaterial, where the system can polymerize monomers to polymer. For thepurposes of this invention and the claims thereto, when catalyst systemsare described as comprising neutral stable forms of the components, itis well understood by one of ordinary skill in the art, that the ionicform of the component is the form that reacts with the monomers toproduce polymers.

In the description herein, the metallocene catalyst may be described asa catalyst precursor, a pre-catalyst compound, or a transition metalcompound, and these terms are used interchangeably. An “anionic ligand”is a negatively charged ligand which donates one or more pairs ofelectrons to a metal ion. A “neutral donor ligand” is a neutrallycharged ligand which donates one or more pairs of electrons to a metalion.

A metallocene catalyst is defined as an organometallic compound with atleast one π-bound cyclopentadienyl moiety (or substitutedcyclopentadienyl moiety) and more frequently two π-boundcyclopentadienyl moieties or substituted cyclopentadienyl moieties. Thisincludes other π-bound moieties such as indenyls or fluorenyls orderivatives thereof.

Catalyst compounds useful herein to produce the vinyl terminatedoligomers include one or more metallocene compound(s) represented by theformulae:

whereHf is hafnium;each X is, independently, selected from the group consisting ofhydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides,alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines,ethers, or a combination thereof, preferably methyl, ethyl, propyl,butyl, phenyl, benzyl, chloride, bromide, iodide, (alternately two X'smay form a part of a fused ring or a ring system);each Q is, independently carbon or a heteroatom, preferably C, N, P, S(preferably at least one Q is a heteroatom, alternately at least two Q'sare the same or different heteroatoms, alternately at least three Q'sare the same or different heteroatoms, alternately at least four Q's arethe same or different heteroatoms);each R¹ is, independently, hydrogen or a C₁ to C₈ alkyl group,preferably a C₁ to C₈ linear alkyl group, preferably methyl ethyl,propyl, butyl, pentyl, hexyl, heptyl, or octyl, R¹ may the same ordifferent as R²;each R² is, independently, hydrogen or a C₁ to C₈ alkyl group,preferably a C₁ to C₈ linear alkyl group, preferably methyl ethyl,propyl, butyl, pentyl, hexyl, heptyl, or octyl, provided that at leastone of R¹ or R² is not hydrogen, preferably both of R¹ and R² are nothydrogen, preferably R¹ and/or R² are not branched;each R³ is, independently, hydrogen, or a substituted or unsubstitutedhydrocarbyl group having from 1 to 8 carbon atoms, preferably 1 to 6carbon atoms, preferably a substituted or unsubstituted C₁ to C₈ linearalkyl group, preferably methyl ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, provided, however, that at least three R³ groups are nothydrogen (alternately four R³ groups are not hydrogen, alternately fiveR³ groups are not hydrogen); {Alternately, when the catalyst compound isto used to make the homo-oligomer then each R³ is, independently,hydrogen, or a substituted or unsubstituted hydrocarbyl group havingfrom 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, preferably asubstituted or unsubstituted C₁ to C₈ linear alkyl group, preferablymethyl ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, providedhowever that: 1) all five R³ groups are methyl; or 2) four R³ groups arenot hydrogen and at least one R³ group is a C₂ to C₈ substituted orunsubstituted hydrocarbyl (preferably at least two, three, four, or fiveR³ groups are a C₂ to C₈ substituted or unsubstituted hydrocarbyl)};each R⁴ is, independently, hydrogen or a substituted or unsubstitutedhydrocarbyl group, a heteroatom or heteroatom containing group,preferably a substituted or unsubstituted hydrocarbyl group having from1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, preferably asubstituted or unsubstituted C₁ to C₈ linear alkyl group, preferablymethyl ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, substitutedphenyl (such as propyl phenyl), phenyl, silyl, substituted silyl, (suchas CH₂SiR′, where R′ is a C₁ to C₁₂ hydrocarbyl, such as methyl, ethyl,propyl, butyl, phenyl);R⁵ is hydrogen or a C₁ to C₈ alkyl group, preferably a C₁ to C₈ linearalkyl group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, or octyl;R⁶ is hydrogen or a C₁ to C₈ alkyl group, preferably a C₁ to C₈ linearalkyl group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, or octyl;each R⁷ is, independently, hydrogen, or a C₁ to C₈ alkyl group,preferably a C₁ to C₈ linear alkyl group, preferably methyl ethyl,propyl, butyl, pentyl, hexyl, heptyl, or octyl, provided however that atleast seven R⁷ groups are not hydrogen, alternately at least eight R⁷groups are not hydrogen, alternately all R⁷ groups are not hydrogen,(preferably the R⁷ groups at the 3 and 4 positions on each Cp ring ofFormula IV are not hydrogen);N is nitrogen;T is a bridge, preferably, Si or Ge, preferably Si;each R^(a), is independently, hydrogen, halogen or a C₁ to C₂₀hydrocarbyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, phenyl, benzyl, substituted phenyl, and two R^(a) canform a cyclic structure including aromatic, partially saturated, orsaturated cyclic or fused ring system; and further provided that any twoadjacent R groups may form a fused ring or multicenter fused ring systemwhere the rings may be aromatic, partially saturated or saturated.

In an alternate embodiment, at least one R⁴ group is not hydrogen,alternately at least two R⁴ groups are not hydrogen, alternately atleast three R⁴ groups are not hydrogen, alternately at least four R⁴groups are not hydrogen, alternately all R⁴ groups are not hydrogen.

Catalyst compounds that are particularly useful in this inventioninclude one or more of:

(1,3-Dimethylindenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,(1,3,4,7-Tetramethylindenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,(1,3-Dimethylindenyl)(tetramethylcyclopentadienyl)hafniumdimethyl,(1,3-Diethylindenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,(1,3-Dipropylindenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,(1-Methyl,3-propyllindenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,(1,3-Dimethylindenyl)(tetramethylpropylcyclopentadienyl)hafniumdimethyl,(1,2,3-Trimethylindenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,(1,3-Dimethylbenzindenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,(2,7-Bis t-butylfluorenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,(9-Methylfluorenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,(2,7,9-Trimethylfluorenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,μ-Dihydrosilyl-bis(tetramethylcyclopentadienyl)hafniumdimethyl,μ-Dimethylsilyl(tetramethylcyclopentadienyl)(3-propyltrimethylcyclopentadienyl)hafniumdimethyl, and μ-Dicyclopropylsilyl(bistetramethylcyclopentadienyl)hafniumdimethyl.

In another embodiment, the vinyl terminated polyolefins useful here inmay be produced using the catalyst compound represented by the formula:

where M is hafnium or zirconium (preferably hafnium); each X is,independently, selected from the group consisting of hydrocarbylradicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides,sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and acombination thereof, (two X's may form a part of a fused ring or a ringsystem) (preferably each X is independently selected from halides and C₁to C₅ alkyl groups, preferably each X is a methyl group); each R⁸ is,independently, a C₁ to C₁₀ alkyl group (preferably methyl, ethyl,propyl, butyl, pentyl, hexyl, or isomers thereof, preferably each R⁸ isa methyl group); each R⁹ is, independently, a C₁ to C₁₀ alkyl group(preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, or isomersthereof, preferably each R⁹ is a n-propyl group); each R¹⁰ is hydrogen;each R¹¹, R¹², and R¹³, is, independently, hydrogen or a substituted orunsubstituted hydrocarbyl group, a heteroatom or heteroatom containinggroup (preferably hydrogen); T is a bridging group (preferably T isdialkyl silicon or dialkyl germanium, preferably T is dimethyl silicon);and further provided that any of adjacent R¹¹, R¹², and R¹³ groups mayform a fused ring or multicenter fused ring system where the rings maybe aromatic, partially saturated or saturated. For further informationon such catalyst compounds and their use to make vinyl terminatedpolyolefins, please see concurrently filed U.S. Ser. No. 13/072,280,filed Mar. 25, 2011 and entitled “Novel Catalysts and Methods of UseThereof to Produce Vinyl Terminated Polymers”.

Catalyst compounds that are particularly useful in this inventioninclude one or more of:

rac-dimethylsilyl bis(2-methyl,3-propylindenyl)hafniumdimethyl,rac-dimethylsilyl bis(2-methyl,3-propylindenyl)zirconiumdimethyl,rac-dimethylsilyl bis(2-ethyl,3-propylindenyl)hafniumdimethyl;rac-dimethylsilyl bis(2-ethyl,3-propylindenyl)zirconiumdimethyl,rac-dimethylsilyl bis(2-methyl,3-ethylindenyl)hafniumdimethyl,rac-dimethylsilyl bis(2-methyl,3-ethylindenyl)zirconiumdimethyl,rac-dimethylsilyl bis(2-methyl,3-isopropylindenyl)hafniumdimethyl,rac-dimethylsilyl bis(2-methyl,3-isopropylindenyl)zirconiumdimethyl,rac-dimethylsilyl bis(2-methyl,3-butyllindenyl)hafniumdimethyl,rac-dimethylsilyl bis(2-methyl,3-butylindenyl)zirconiumdimethyl,rac-dimethylgermanyl bis(2-methyl,3-propylindenyl)hafniumdimethyl,rac-dimethylgermanyl bis(2-methyl,3-propylindenyl)zirconiumdimethyl,rac-dimethylgermanyl bis(2-ethyl,3-propylindenyl)hafniumdimethyl,rac-dimethylgermanyl bis(2-ethyl,3-propylindenyl)zirconiumdimethyl,rac-dimethylgermanyl bis(2-methyl,3-ethylindenyl)hafniumdimethyl,rac-dimethylgermanyl bis(2-methyl,3-ethylindenyl)zirconiumdimethyl,rac-dimethylgermanyl bis(2-methyl,3-isopropylindenyl)hafniumdimethyl,rac-dimethylgermanyl bis(2-methyl,3-isopropylindenyl)zirconiumdimethyl,rac-dimethylgermanyl bis(2-methyl,3-butyllindenyl)hafniumdimethyl,rac-dimethylgermanyl bis(2-methyl,3-propylindenyl)zirconiumdimethyl,rac-dimethylsilyl bis(2-propyl,3-methylindenyl)hafniumdimethyl,rac-dimethylsilyl bis(2-propyl,3-methylindenyl)zirconiumdimethyl,rac-dimethylsilyl bis(2-propyl,3-ethylindenyl)hafniumdimethyl,rac-dimethylsilyl bis(2-propyl,3-ethylindenyl)zirconiumdimethyl,rac-dimethylsilylbis(2-propyl,3-butylindenyl)hafniumdimethyl,rac-dimethylsilylbis(2-propyl,3-butylindenyl)zirconiumdimethyl,rac-dimethylsilyl bis(2-methyl,3-butylindenyl)hafniumdimethyl,rac-dimethylsilyl bis(2-methyl,3-butylindenyl)zirconiumdimethyl,rac-dimethylsilyl bis(2,3-dimethyl)hafniumdimethyl, rac-dimethylsilylbis(2,3-dimethyl)zirconiumdimethyl, rac-dimethylgermanylbis(2-propyl,3-methylindenyl)hafniumdimethyl, rac-dimethylgermanylbis(2-propyl,3-methylindenyl)zirconiumdimethyl, rac-dimethylgermanylbis(2-propyl,3-ethylindenyl)hafniumdimethyl, rac-dimethylgermanylbis(2-propyl,3-ethylindenyl)zirconiumdimethyl, rac-dimethylgermanylbis(2-propyl,3-butylindenyl)hafniumdimethyl, rac-dimethylgermanylbis(2-propyl,3-butylindenyl)zirconiumdimethyl, rac-dimethylgermanylbis(2-methyl,3-butylindenyl)hafniumdimethyl, rac-dimethylgermanylbis(2-methyl,3-butylindenyl)zirconiumdimethyl, rac-dimethylgermanylbis(2,3-dimethyl)hafniumdimethyl, and rac-dimethylgermanylbis(2,3-dimethyl)zirconiumdimethyl.

In an alternate embodiment, the “dimethyl” after the transition metal inthe list of catalyst compounds above is replaced with a dihalide (suchas dichloride or difluoride) or a bisphenoxide, particularly for usewith an alumoxane activator.

In particular embodiments, the catalyst compound israc-dimethylsilylbis(2-methyl,3-propylindenyl)hafniumdimethyl ordichloride, orrac-dimethylsilylbis(2-methyl,3-propylindenyl)zirconiumdimethyl ordichloride.

Preferred activators useful with the above include:dimethylaniliniumtetrakis(pentafluorophenyl)borate,dimethylaniliniumtetrakis(heptafluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,tropillium tetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate,benzene(diazonium)tetrakis(perfluorobiphenyl)borate, and[4-t-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B] (where Ph is phenyl and Me ismethyl).

Preferred combinations of catalyst and activator include:N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate andrac-dimethylsilylbis(2-methyl,3-propylindenyl)hafniumdimethyl, orrac-dimethylsilylbis(2-methyl,3-propylindenyl)zirconiumdimethyl.

In another embodiment, the vinyl terminated polyolefins useful here inmay be produced using the catalyst compound represented by the formula:

wherein M is hafnium or zirconium; each X is, independently, selectedfrom the group consisting of hydrocarbyl radicals having from 1 to 20carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides,halogens, dienes, amines, phosphines, ethers, or a combination thereof;each R¹⁵ and R¹⁷ are, independently, a C₁ to C₈ alkyl group (preferablya C₁ to C₈ linear alkyl group, preferably methyl ethyl, propyl, butyl,pentyl, hexyl, heptyl, or octyl); and each R¹⁶, R¹⁸, R¹⁹, R²⁰, R²¹, R²²,R²³, R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸ are, independently, hydrogen, or asubstituted or unsubstituted hydrocarbyl group having from 1 to 8 carbonatoms (preferably 1 to 6 carbon atoms, preferably a substituted orunsubstituted C₁ to C₈ linear alkyl group, preferably methyl ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl). In a preferred embodiment,at least three of R²⁴-R²⁸ groups are not hydrogen (alternately four ofR²⁴-R²⁸ groups are not hydrogen, alternately five of R²⁴-R²⁸ groups arenot hydrogen). In a preferred embodiment, all five groups of R²⁴-R²⁸ aremethyl. In a preferred embodiment, four of the R²⁴-R²⁸ groups are nothydrogen and at least one of the R²⁴-R²⁸ groups is a C₂ to C₈substituted or unsubstituted hydrocarbyl (preferably at least two,three, four or five of R²⁴-R²⁸ groups are a C₂ to C₈ substituted orunsubstituted hydrocarbyl). In another preferred embodiment, R¹⁵ and R¹⁷are methyl groups, R¹⁶ is a hydrogen, R¹⁸-R²³ are all hydrogens, R²⁴-R²⁸are all methyl groups, and each X is a methyl group. For furtherinformation on such catalyst compounds and their use to make vinylterminated polyolefins, please see concurrently filed U.S. Ser. No.13/072,279, filed Mar. 25, 2011 and entitled “Enhanced CatalystPerformance for Production of Vinyl Terminated Propylene andEthylene/Propylene Macromers.”

Catalyst compounds that are particularly useful in this inventioninclude (CpMe₅)(1,3-Me₂-benz[e] indenyl)HfMe₂,(CpMe₅)(1-methyl-3-n-propylbenz[e] indenyl)HfMe₂,(CpMe₅)(1-n-propyl,3-methylbenz[e] indenyl)HfMe₂,(CpMe₅)(1-methyl-3-n-butylbenz[e] indenyl)HfMe₂,(CpMe₅)(1-n-butyl,3-methylbenz[e] indenyl)HfMe₂,(CpMe₅)(1-ethyl,3-methylbenz[e] indenyl)HfMe₂, (CpMe₅)(1-methyl,3-ethylbenz[e] indenyl)HfMe₂, (CpMe₄n-propyl)(1,3-Me₂-benz[e]indenyl)HfMe₂, (CpMe₄-n-propyl)(1-methyl-3-n-propylbenz[e]indenyl)HfMe₂, (CpMe₄-n-propyl)(1-n-propyl,3-methylbenz[e]indenyl)HfMe₂, (CpMe₄-n-propyl)(1-methyl-3-n-butylbenz[e] indenyl)HfMe₂,(CpMe₄-n-propyl)(1-n-butyl,3-methylbenz[e] indenyl)HfMe₂,(CpMe₄-n-propyl)(1-ethyl,3-methylbenz[e] indenyl)HfMe₂,(CpMe₄-n-propyl)(1-methyl, 3-ethylbenz[e] indenyl)HfMe₂,(CpMe₄n-butyl)(1,3-Me₂-benz[e] indenyl)HfMe₂,(CpMe₄n-butyl)(1-methyl-3-n-propylbenz[e] indenyl)HfMe₂,(CpMe₄n-butyl)(1-n-propyl,3-methylbenz[e] indenyl)HfMe₂,(CpMe₄n-butyl)(1-methyl-3-n-butylbenz[e] indenyl)HfMe₂,(CpMe₄n-butyl)(1-n-butyl,3-methylbenz[e] indenyl)HfMe₂,(CpMe₄n-butyl)(1-ethyl,3-methylbenz[e] indenyl)HfMe₂,(CpMe₄n-butyl)(1-methyl, 3-ethylbenz[e] indenyl)HfMe₂, and the zirconiumanalogs thereof.

In an alternate embodiment, the “dimethyl” (Me₂) after the transitionmetal in the list of catalyst compounds above is replaced with adihalide (such as dichloride or difluoride) or a bisphenoxide,particularly for use with an alumoxane activator.

Other activators useful with the above catalysts include:dimethylaniliniumtetrakis(pentafluorophenyl)borate,dimethylaniliniumtetrakis(heptafluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,tropillium tetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate,benzene(diazonium)tetrakis(perfluorobiphenyl)borate,[4-t-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B].

In a preferred embodiment the branched polymers described herein may beproduced as described in concurrently filed U.S. Ser. No. 61/467,681filed Mar. 25, 2011, and entitled “Branched Vinyl Terminated Polymersand Methods for Production Thereof”.

Activators and Activation Methods for Catalyst Compounds to Make VinylTerminated Polymers

The terms “cocatalyst” and “activator” are used herein interchangeablyand are defined to be any compound which can activate any one of thecatalyst compounds described above by converting the neutral catalystcompound to a catalytically active catalyst compound cation.Non-limiting activators, for example, include alumoxanes, aluminumalkyls, ionizing activators, which may be neutral or ionic, andconventional-type cocatalysts. Preferred activators typically includealumoxane compounds, modified alumoxane compounds, and ionizing anionprecursor compounds that abstract one reactive, σ-bound, metal ligandmaking the metal complex cationic and providing a charge-balancingnoncoordinating or weakly coordinating anion.

In one embodiment, alumoxane activators are utilized as an activator inthe catalyst composition. Alumoxanes are generally oligomeric compoundscontaining —Al(R¹)—O— sub-units, where R¹ is an alkyl group. Examples ofalumoxanes include methylalumoxane (MAO), modified methylalumoxane(MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes andmodified alkylalumoxanes are suitable as catalyst activators,particularly when the abstractable ligand is an alkyl, halide, alkoxide,or amide. Mixtures of different alumoxanes and modified alumoxanes mayalso be used. It may be preferable to use a visually clearmethylalumoxane. A cloudy or gelled alumoxane can be filtered to producea clear solution or clear alumoxane can be decanted from the cloudysolution. Another alumoxane is a modified methyl alumoxane (MMAO)cocatalyst type 3A (commercially available from Akzo Chemicals, Inc.under the trade name Modified Methylalumoxane type 3A, covered underU.S. Pat. No. 5,041,584).

When the activator is an alumoxane (modified or unmodified), someembodiments select the maximum amount of activator at a 5000-fold molarexcess Al/M over the catalyst precursor (per metal catalytic site). Theminimum activator-to-catalyst-precursor is a 1:1 molar ratio. Alternatepreferred ranges include up to 500:1, alternately up to 200:1,alternately up to 100:1, alternately from 1:1 to 50:1.

Aluminum alkyl or organoaluminum compounds which may be utilized asco-activators (or scavengers) include trimethylaluminum,triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, and the like.

Ionizing Activators

It is within the scope of this invention to use an ionizing orstoichiometric activator, neutral or ionic, such as tri (n-butyl)ammonium tetrakis (pentafluorophenyl) borate, a tris perfluorophenylboron metalloid precursor or a tris perfluoronaphthyl boron metalloidprecursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid(U.S. Pat. No. 5,942,459), or combination thereof. It is also within thescope of this invention to use neutral or ionic activators alone or incombination with alumoxane or modified alumoxane activators. Morepreferred activators include the ionic activators.

Examples of neutral stoichiometric activators include tri-substitutedboron, tellurium, aluminum, gallium, and indium, or mixtures thereof.The three substituent groups are each independently selected fromalkyls, alkenyls, halogens, substituted alkyls, aryls, arylhalides,alkoxy, and halides. Preferably, the three groups are independentlyselected from halogen, mono or multicyclic (including halosubstituted)aryls, alkyls, and alkenyl compounds, and mixtures thereof, preferredare alkenyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms and arylgroups having 3 to 20 carbon atoms (including substituted aryls). Morepreferably, the three groups are alkyls having 1 to 4 carbon groups,phenyl, napthyl, or mixtures thereof. Even more preferably, the threegroups are halogenated, preferably fluorinated, aryl groups. Mostpreferably, the neutral stoichiometric activator is tris perfluorophenylboron or tris perfluoronaphthyl boron.

Ionic stoichiometric activator compounds may contain an active proton,or some other cation associated with, but not coordinated to, or onlyloosely coordinated to, the remaining ion of the ionizing compound. Suchcompounds and the like are described in European publications EP 0 570982 A; EP 0 520 732 A; EP 0 495 375 A; EP 0 500 944 B1; EP 0 277 003 A;EP 0 277 004 A; U.S. Pat. Nos. 5,153,157; 5,198,401; 5,066,741;5,206,197; 5,241,025; 5,384,299; 5,502,124; and U.S. patent applicationSer. No. 08/285,380, filed Aug. 3, 1994; all of which are herein fullyincorporated by reference.

Ionic catalysts can be preparedly reacting a transition metal compoundwith some neutral Lewis acids, such as B(C₆F₆)₃, which upon reactionwith the hydrolyzable ligand (X) of the transition metal compound formsan anion, such as ([B(C₆F₅)₃(X)]⁻), which stabilizes the cationictransition metal species generated by the reaction. The catalysts canbe, and preferably are, prepared with activator components which areionic compounds or compositions.

Compounds useful as an activator component in the preparation of theionic catalyst systems used in the process of this invention comprise acation, which is preferably a Bronsted acid capable of donating aproton, and a compatible non-coordinating anion which anion isrelatively large (bulky), capable of stabilizing the active catalystspecies (the Group 4 cation) which is formed when the two compounds arecombined and said anion will be sufficiently labile to be displaced byolefinic, diolefinic and acetylenically unsaturated substrates or otherneutral Lewis bases such as ethers, amines, and the like. Two classes ofcompatible non-coordinating anions have been disclosed in EP 0 277,003 Aand EP 0 277,004 A, published 1988: 1) anionic coordination complexescomprising a plurality of lipophilic radicals covalently coordinated toand shielding a central charge-bearing metal or metalloid core; and 2)anions comprising a plurality of boron atoms such as carboranes,metallacarboranes and boranes.

In a preferred embodiment, the stoichiometric activators include acation and an anion component, and may be represented by the followingformula:(L-H)_(d) ⁺(A^(d−))  (14)wherein L is an neutral Lewis base; H is hydrogen; (L-H)⁺ is a Bronstedacid; A^(d−) is a non-coordinating anion having the charge d−; and d isan integer from 1 to 3.

The cation component, (L-H)_(d) ⁺ may include Bronsted acids such asprotonated Lewis bases capable of protonating a moiety, such as an alkylor aryl, from the bulky ligand metallocene containing transition metalcatalyst precursor, resulting in a cationic transition metal species.

The activating cation (L-H)_(d) ⁺ may be a Bronsted acid, capable ofdonating a proton to the transition metal catalytic precursor resultingin a transition metal cation, including ammoniums, oxoniums,phosphoniums, silyliums, and mixtures thereof, preferably ammoniums ofmethylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline,methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline,p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine,triphenylphosphine, and diphenylphosphine, oxoniums from ethers, such asdimethyl ether diethyl ether, tetrahydrofuran, and dioxane, sulfoniumsfrom thioethers, such as diethyl thioethers and tetrahydrothiophene, andmixtures thereof.

The anion component A^(d−) include those having the formula [M^(k+Q)_(n)]^(d−) wherein k is an integer from 1 to 3; n is an integer from 2to 6; n−k=d; M is an element selected from Group 13 of the PeriodicTable of the Elements, preferably boron or aluminum; and Q isindependently a hydride, bridged or unbridged dialkylamido, halide,alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Qhaving up to 20 carbon atoms with the proviso that in not more than 1occurrence is Q a halide. Preferably, each Q is a fluorinatedhydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q isa fluorinated aryl group, and most preferably each Q is a pentafluorylaryl group. Examples of suitable A^(d−) also include diboron compoundsas disclosed in U.S. Pat. No. 5,447,895, which is fully incorporatedherein by reference.

Illustrative, but not limiting examples of boron compounds which may beused as an activating cocatalyst in the preparation of the improvedcatalysts of this invention are tri-substituted ammonium salts such as:

trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate,tripropylammonium tetraphenylborate, tri(n-butyl)ammoniumtetraphenylborate, tri(t-butyl)ammonium tetraphenylborate,N,N-dimethylanilinium tetraphenylborate, N,N-diethylaniliniumtetraphenylborate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate, tropilliumtetraphenylborate, triphenylcarbenium tetraphenylborate,triphenylphosphonium tetraphenylborate, triethylsilyliumtetraphenylborate, benzene(diazonium)tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,tropillium tetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate,benzene(diazonium)tetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluoro-phenyl)borate, dimethyl(t-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,tropillium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triphenylphosphonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triethylsilylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,tropillium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate,benzene(diazonium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,tropillium tetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate,benzene(diazonium)tetrakis(perfluorobiphenyl)borate, trimethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tripropylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(t-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-diethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tropillium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylphosphonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triethylsilylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,dialkyl ammonium salts, such as: di-(i-propyl)ammoniumtetrakis(pentafluorophenyl)borate, dicyclohexylammoniumtetrakis(pentafluorophenyl)borate, and additional tri-substitutedphosphonium salts, such as tri(o-tolyl)phosphoniumtetrakis(pentafluorophenyl)borate, andtri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate.

Most preferably, the ionic stoichiometric activator (L-H)_(d) ⁺ (A^(d−))is N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-b is(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbeniumtetrakis(perfluorophenyl)borate.

In one embodiment, an activation method using ionizing ionic compoundsnot containing an active proton but capable of producing a bulky ligandmetallocene catalyst cation and their non-coordinating anion are alsocontemplated, and are described in EP 0 426 637 A; EP 0 573 403 A; andU.S. Pat. No. 5,387,568, which are all herein incorporated by reference.

The term “non-coordinating anion” (NCA) means an anion which either doesnot coordinate to said cation or which is only weakly coordinated tosaid cation thereby remaining sufficiently labile to be displaced by aneutral Lewis base. “Compatible” non-coordinating anions are those whichare not degraded to neutrality when the initially formed complexdecomposes. Further, the anion will not transfer an anionic substituentor fragment to the cation so as to cause it to form a neutral fourcoordinate metallocene compound and a neutral by-product from the anion.Non-coordinating anions useful in accordance with this invention arethose that are compatible, stabilize the metallocene cation in the senseof balancing its ionic charge at +1, yet retain sufficient lability topermit displacement by an ethylenically or acetylenically unsaturatedmonomer during polymerization. In addition to these activator compoundsor co-catalysts, scavengers are used, such as tri-isobutyl aluminum ortri-octyl aluminum.

Invention process also can employ cocatalyst compounds or activatorcompounds that are initially neutral Lewis acids but form a cationicmetal complex and a noncoordinating anion, or a zwitterionic complexupon reaction with the invention compounds. For example,tris(pentafluorophenyl)boron or aluminum act to abstract a hydrocarbylor hydride ligand to yield an invention cationic metal complex andstabilizing noncoordinating anion, see EP 0 427 697 A and EP 0 520 732 Afor illustrations of analogous Group-4 metallocene compounds. Also, seethe methods and compounds of EP 0 495 375 A. For formation ofzwitterionic complexes using analogous Group 4 compounds, see U.S. Pat.Nos. 5,624,878; 5,486,632; and 5,527,929.

Another suitable ion forming, activating cocatalyst comprises a salt ofa cationic oxidizing agent and a noncoordinating, compatible anionrepresented by the formula:(OX^(e+))_(d)(A^(d−))_(e)  (16)wherein OX^(e+) is a cationic oxidizing agent having a charge of e+; eis an integer from 1 to 3; and A⁻, and d are as previously defined.Examples of cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag⁺, or Pb⁺². Preferred embodimentsof A^(d−) are those anions previously defined with respect to theBronsted acid containing activators, especiallytetrakis(pentafluorophenyl)borate.

The typical activator-to-catalyst-precursor ratio when the activator isnot analumoxane is a 1:1 molar ratio. Alternate preferred ranges includefrom 0.1:1 to 100:1, alternately from 0.5:1 to 200:1, alternately from1:1 to 500:1 alternately from 1:1 to 1000:1. A particularly useful rangeis from 0.5:1 to 10:1, preferably 1:1 to 5:1.

Particularly useful activators include bulky activators. “Bulkyactivator” as used herein refers to anionic activators represented bythe formula:

where:each R₁ is, independently, a halide, preferably a fluoride;each R₂ is, independently, a halide, a C₆ to C₂₀ substituted aromatichydrocarbyl group or a siloxy group of the formula —O—Si—R_(a), whereR_(a) is a C₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl group (preferablyR₂ is a fluoride or a perfluorinated phenyl group);each R₃ is a halide, C₆ to C₂₀ substituted aromatic hydrocarbyl group ora siloxy group of the formula —O—Si—R_(a), where R_(a) is a C₁ to C₂₀hydrocarbyl or hydrocarbylsilyl group (preferably R₃ is a fluoride or aC₆ perfluorinated aromatic hydrocarbyl group); wherein R₂ and R₃ canform one or more saturated or unsaturated, substituted or unsubstitutedrings (preferably R₂ and R₃ form a perfluorinated phenyl ring);L is an neutral Lewis base;(L-H)⁺is a Bronsted acid;d is 1, 2, or 3;wherein the anion has a molecular weight of greater than 1020 g/mol; andwherein at least three of the substituents on the B atom each have amolecular volume of greater than 250 cubic Å, alternately greater than300 cubic Å, or alternately greater than 500 cubic Å.

“Molecular volume” is used herein as an approximation of spatial stericbulk of an activator molecule in solution. Comparison of substituentswith differing molecular volumes allows the substituent with the smallermolecular volume to be considered “less bulky” in comparison to thesubstituent with the larger molecular volume. Conversely, a substituentwith a larger molecular volume may be considered “more bulky” than asubstituent with a smaller molecular volume.

Molecular volume may be calculated as reported in “A Simple ‘Back of theEnvelope’ Method for Estimating the Densities and Molecular Volumes ofLiquids and Solids,” Journal of Chemical Education, Vol. 71, No. 11,November 1994, pp. 962-964. Molecular volume (MV), in units of cubic Å,is calculated using the formula: MV=8.3V_(S), where V_(S) is the scaledvolume. V_(S) is the sum of the relative volumes of the constituentatoms, and is calculated from the molecular formula of the substituentusing the following table of relative volumes. For fused rings, theV_(S) is decreased by 7.5% per fused ring.

Element Relative Volume H 1 1^(st) short period, Li to F 2 2^(nd) shortperiod, Na to Cl 4 1^(st) long period, K to Br 5 2^(nd) long period, Rbto I 7.5 3^(rd) long period, Cs to Bi 9

Exemplary bulky substituents of activators suitable herein and theirrespective scaled volumes and molecular volumes are shown in the tablebelow. The dashed bonds indicate binding to boron, as in the generalformula above.

Molecular MV Formula Per Structure of of each subst. Total MV Activatorboron substituents substituent V_(S) (Å³) (Å³) Dimethylaniliniumtetrakis(perfluoronaphthyl)borate

C₁₀F₇ 34 261 1044 Dimethylanilinium tetrakis(perfluorobiphenyl)borate

C₁₂F₉ 42 349 1396 [4-tButyl-PhNMe₂H] [(C₆F₃(C₆F₅)₂)₄B]

C₁₈F₁₃ 62 515 2060

Exemplary bulky activators useful in catalyst systems herein include:

trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,tropillium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate,benzene(diazonium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,tropillium tetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate,benzene(diazonium)tetrakis(perfluorobiphenyl)borate,[4-t-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B], and the types disclosed in U.S.Pat. No. 7,297,653.Activator Combinations

It is within the scope of this invention that catalyst compounds can becombined with one or more activators or activation methods describedabove. For example, a combination of activators have been described inU.S. Pat. Nos. 5,153,157; 5,453,410; European publication EP 0 573 120B1; PCT publications WO 94/07928; and WO 95/14044. These documents alldiscuss the use of an alumoxane in combination with an ionizingactivator.

Support Materials

In embodiments herein, the catalyst system used to make the vinylterminated polyolefins may comprise an inert support material.Preferably the supported material is a porous support material, forexample, talc, and inorganic oxides. Other support materials includezeolites, clays, organoclays, or any other organic or inorganic supportmaterial and the like, or mixtures thereof.

Preferably, the support material is an inorganic oxide in a finelydivided form. Suitable inorganic oxide materials for use in metallocenecatalyst systems herein include Groups 2, 4, 13, and 14 metal oxidessuch as silica, alumina and mixtures thereof. Other inorganic oxidesthat may be employed either alone or in combination with the silica, oralumina are magnesia, titania, zirconia, and the like. Other suitablesupport materials, however, can be employed, for example, finely dividedfunctionalized multiblock polyolefins such as finely dividedpolyethylene. Particularly useful supports include magnesia, titania,zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays, andthe like. Also, combinations of these support materials may be used, forexample, silica-chromium, silica-alumina, silica-titania and the like.Preferred support materials include Al₂O₃, ZrO₂, SiO₂, and combinationsthereof, more preferably SiO₂, Al₂O₃, or SiO₂/Al₂O₃

It is preferred that the support material, most preferably an inorganicoxide, has a surface area in the range of from about 10 to about 700m²/g, pore volume in the range of from about 0.1 to about 4.0 cc/g andaverage particle size in the range of from about 5 to about 500 μm. Morepreferably, the surface area of the support material is in the range offrom about 50 to about 500 m²/g, pore volume of from about 0.5 to about3.5 cc/g and average particle size of from about 10 to about 200 μm.Most preferably the surface area of the support material is in the rangeis from about 100 to about 400 m²/g, pore volume from about 0.8 to about3.0 cc/g and average particle size is from about 5 to about 100 μm. Theaverage pore size of the support material useful in the invention is inthe range of from 10 to 1000 Å, preferably 50 to about 500 Å, and mostpreferably 75 to about 350 Å. In some embodiments, the support materialis a high surface area, amorphous silica (surface area=300 m²/gm; porevolume of 1.65 cm³/gm), examples of which are marketed under thetradenames of DAVISON 952 or DAVISON 955 by the Davison ChemicalDivision of W.R. Grace and Company. In other embodiments, DAVISON 948 isused.

The support material should be dry, that is, free of absorbed water.Drying of the support material can be effected by heating or calciningat about 100° C. to about 1000° C., preferably at least about 600° C.When the support material is silica, it is heated to at least 200° C.,preferably about 200° C. to about 850° C., and most preferably at about600° C.; and for a time of about 1 minute to about 100 hours, from about12 hours to about 72 hours, or from about 24 hours to about 60 hours.The calcined support material must have at least some reactive hydroxyl(OH) groups to produce the catalyst system of this invention. Thecalcined support material is then contacted with at least onepolymerization catalyst comprising at least one metallocene compound andan activator.

Methods of Making the Supported Catalyst Systems

The support material, having reactive surface groups, typically hydroxylgroups, is slurried in a non-polar solvent and the resulting slurry iscontacted with a solution of a metallocene compound and an activator.The slurry of the support material in the solvent is prepared byintroducing the support material into the solvent, and heating themixture to about 0° C. to about 70° C., preferably to about 25° C. toabout 60° C., preferably at room temperature. Contact times typicallyrange from about 0.5 hours to about 24 hours, from about 0.5 hours toabout 8 hours, or from about 0.5 hours to about 4 hours.

Suitable non-polar solvents are materials in which all of the reactantsused herein, i.e., the activator, and the metallocene compound, are atleast partially soluble and which are liquid at reaction temperatures.Preferred non-polar solvents are alkanes, such as isopentane, hexane,n-heptane, octane, nonane, and decane, although a variety of othermaterials including cycloalkanes, such as cyclohexane, aromatics, suchas benzene, toluene and ethylbenzene, may also be employed.

In embodiments herein, the support material is contacted with a solutionof a metallocene compound and an activator, such that the reactivegroups on the support material are titrated, to form a supportedpolymerization catalyst. The period of time for contact between themetallocene compound, the activator, and the support material is as longas is necessary to titrate the reactive groups on the support material.To “titrate” is meant to react with available reactive groups on thesurface of the support material, thereby reducing the surface hydroxylgroups by at least 80%, at least 90%, at least 95%, or at least 98%. Thesurface reactive group concentration may be determined based on thecalcining temperature and the type of support material used. The supportmaterial calcining temperature affects the number of surface reactivegroups on the support material available to react with the metallocenecompound and an activator: the higher the drying temperature, the lowerthe number of sites. For example, where the support material is silicawhich, prior to the use thereof in the first catalyst system synthesisstep, is dehydrated by fluidizing it with nitrogen and heating at about600° C. for about 16 hours, a surface hydroxyl group concentration ofabout 0.7 millimoles per gram (mmols/gm) is typically achieved. Thus,the exact molar ratio of the activator to the surface reactive groups onthe carrier will vary. Preferably, this is determined on a case-by-casebasis to assure that only so much of the activator is added to thesolution as will be deposited onto the support material without leavingexcess of the activator in the solution.

The amount of the activator which will be deposited onto the supportmaterial without leaving excess in the solution can be determined in anyconventional manner, e.g., by adding the activator to the slurry of thecarrier in the solvent, while stirring the slurry, until the activatoris detected as a solution in the solvent by any technique known in theart, such as by ¹H NMR. For example, for the silica support materialheated at about 600° C., the amount of the activator added to the slurryis such that the molar ratio of B to the hydroxyl groups (OH) on thesilica is about 0.5:1 to about 4:1, preferably about 0.8:1 to about 3:1,more preferably about 0.9:1 to about 2:1 and most preferably about 1:1.The amount of boron on the silica may be determined by using ICPES(Inductively Coupled Plasma Emission Spectrometry), which is describedin J. W. Olesik, “Inductively Coupled Plasma-Optical EmissionSpectroscopy,” in the Encyclopedia of Materials Characterization, C. R.Brundle, C. A. Evans, Jr. and S. Wilson, Eds., Butterworth-Heinemann,Boston, Mass., 1992, pp. 633-644. In another embodiment, it is alsopossible to add such an amount of activator which is in excess of thatwhich will be deposited onto the support, and then remove, e.g., byfiltration and washing, any excess of the activator.

The following paragraphs provide for various aspects of the presentinvention.

1. A composition comprising a functionalized multiblock polyolefinrepresented by the formula (X) or (XX):PO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(O)—O—((CR¹⁵R¹⁶)_(z)—(CR¹⁷R¹⁸)_(m)—O)_(n)—R¹⁹  (X)orPO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(O)—O—((CR¹⁵R¹⁶)_(z)—(CR¹⁷R¹⁸)_(m)O)_(n)—C(O)—C(R¹⁴)═C(R¹³)—C(R¹²)(R¹¹)—PO  (XX),wherein R¹¹, R¹², R¹³, and R¹⁴ are each independently a substituted orunsubstituted C₁ through C₄ hydrocarbyl group (preferably substituted orunsubstituted methyl, ethyl, propyl, butyl and isomers thereof) or ahydrogen;R¹⁵, R¹⁶, R¹⁷, and R¹⁸ are each independently a substituted orunsubstituted C₁ through C₄ hydrocarbyl group (preferably substituted orunsubstituted methyl, ethyl, propyl, butyl, and isomers thereof) or ahydrogen;R¹⁹ is a C₁ to a C₂₀ substituted or unsubstituted hydrocarbyl group(preferably substituted or unsubstituted methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl, docecyl and isomersthereof), or a hydrogen;z is ≧1 to about 5, preferably 2, 3, 4, or 5;m is ≧1 to about 5, preferably 2, 3, 4, or 5;PO is a polyolefin hydrocarbyl group comprising 10 to 4000 carbon atoms(preferably 15 to 3500, preferably 100 to 2500; andn is from 1 to about 10,000, preferably 2 to 1000, preferably 3 to 500,preferably 4 to 300, preferably 4 to 150, preferably 4 to 50, preferably4 to 20.2. The functionalized multiblock polyolefin of paragraph 1, wherein R¹¹,R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ are each hydrogen atoms and R¹⁹ isa hydrogen, a methyl, or an ethyl group.3. The functionalized multiblock polyolefin of either of paragraphs 1 or2, wherein z is l, m is 1, and n is from 2 to about 1000.4. The functionalized multiblock polyolefin of either of paragraphs 1 or2, wherein z is 2, m is 1, and n is from 2 to about 1000.5. The functionalized multiblock polyolefin of either of paragraphs 1 or2, wherein z is 2, m is 2, and n is from 2 to about 1000.6. The functionalized multiblock polyolefin of any of paragraphs 1through 5, wherein:a) R¹¹ through R¹⁴ are all hydrogens and one of R¹⁵ through R¹⁸ is aC₁-C₆ hydrocarbon: orb) R¹² through R¹⁸ comprise six hydrogens and one C₁-C₆ hydrocarbon; orc) R¹² through R¹⁸ comprise six hydrogens and one methyl group.7. The functionalized multiblock polyolefin of any of paragraphs 1through 6, wherein the functionalized multiblock polyolefin isamphiphilic, preferably n is greater than 1, preferably from 1 to 100,and PO is a hydrocarbyl or a substituted hydrocarbyl, provided that ifPO is a substituted hydrocarbyl, then PO is not water soluble,preferably, one of “(CR¹⁷R¹⁸)_(m)—O)_(n)” or PO in Formula (X) or (XX)is hydrophobic and the other is hydrophilic.8. A process to prepare the functionalized multiblock polyolefin of anyof paragraphs 1 to 7 comprising contacting: 1) an alkene metathesiscatalyst, 2) an acrylate or methacrylate functionalized polyalkyleneglycol represented by the formula (XII) or (XaII):C(R¹³)(R²⁰)═C(R¹⁴)—C(O)—O—((CR¹⁵R¹⁶)_(z)—(CR¹⁷R¹⁸)_(m)—O)_(n)—R¹⁹  (XII)orC(R¹³)(R²⁰)═C(R¹⁴)—C(O)—O—((CR¹⁵R¹⁶)_(z)—(CR¹⁷R¹⁸)_(m)—(O)_(n)—C(O)—C(R¹⁴)═C(R¹³)(R²⁰)  (XXII)wherein R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, z, m, and n are as definedabove in paragraph 1; R²⁰ is a hydrogen or a C₁ to a C₄ substituted orunsubstituted hydrocarbyl group (preferably substituted or unsubstitutedmethyl, ethyl, propyl, butyl and isomers thereof); and 3) a vinylterminated polyolefin, preferably containing at least 5% allyl chainends, relative to total unsaturation.9. The process of paragraph 8, wherein the vinyl terminated polyolefinis one or more of: a) a propylene co-oligomer having an Mn of 300 to30,000 g/mol (as measured by ¹H NMR) comprising 10 to 90 mol % propyleneand 10 to 90 mol % of ethylene, wherein the oligomer has at least X %allyl chain ends (relative to total unsaturations), where: 1) X=(−0.94(mol % ethylene incorporated)+100), when 10 to 60 mol % ethylene ispresent in the co-oligomer, and 2) X=45, when greater than 60 and lessthan 70 mol % ethylene is present in the co-oligomer, and 3)X=(1.83*(mol % ethylene incorporated)−83), when 70 to 90 mol % ethyleneis present in the co-oligomer; and/orb) a propylene oligomer, comprising more than 90 mol % propylene andless than 10 mol % ethylene, wherein the oligomer has: at least 93%allyl chain ends, an Mn of about 500 to about 20,000 g/mol (as measuredby ¹H NMR), an isobutyl chain end to allylic vinyl group ratio of 0.8:1to 1.35:1.0, and less than 1400 ppm aluminum; and/orc) a propylene oligomer, comprising at least 50 mol % propylene and from10 to 50 mol % ethylene, wherein the oligomer has: at least 90% allylchain ends, Mn of about 150 to about 10,000 g/mol (as measured by ¹HNMR), and an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to1.3:1.0, wherein monomers having four or more carbon atoms are presentat from 0 to 3 mol %; and/ord) a propylene oligomer, comprising at least 50 mol % propylene, from0.1 to 45 mol % ethylene, and from 0.1 to 5 mol % C₄ to C₁₂ olefin,wherein the oligomer has: at least 87% allyl chain ends (alternately atleast 90%), an Mn of about 150 to about 10,000 g/mol, (as measured by ¹HNMR), and an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to1.35:1.0; and/ore) a propylene oligomer, comprising at least 50 mol % propylene, from0.1 to 45 mol % ethylene, and from 0.1 to 5 mol % diene, wherein theoligomer has: at least 90% allyl chain ends, an Mn of about 150 to about10,000 g/mol (as measured by ¹H NMR), and an isobutyl chain end toallylic vinyl group ratio of 0.7:1 to 1.35:1.0; and/orf) a homooligomer, comprising propylene, wherein the oligomer has: atleast 93% allyl chain ends, an Mn of about 500 to about 20,000 g/mol (asmeasured by ¹H NMR), an isobutyl chain end to allylic vinyl group ratioof 0.8:1 to 1.2:1.0, and less than 1400 ppm aluminum; and/org) a branched polyolefin having an Mn (¹H NMR) of 7,500 to 60,000 g/molcomprising: (i) one or more alpha olefin derived units selected from thegroup consisting of ethylene and propylene; (ii) 50% or greater allylchain ends, relative to total number of unsaturated chain ends; and(iii) a g′(vis) of 0.90 or less; and/orh) branched polyolefins having an Mn greater than 60,000 g/molcomprising: (i) one or more alpha olefins selected from the groupconsisting of ethylene and propylene; (ii) 50% or greater allyl chainends, relative to total unsaturated chain ends; (iii) a g′(vis) of 0.90or less; and (iv) a bromine number which, upon complete hydrogenation,decreases by at least 50%; and/ori) a branched polyolefins having an Mn of less than 7,500 g/molcomprising: (i) one or more alpha olefin derived units selected from thegroup consisting of ethylene and propylene; (ii) a ratio of percentageof saturated chain ends to percentage of allyl chain ends of 1.2 to 2.0;and (iii) 50% or greater allyl chain ends, relative to total moles ofunsaturated chain ends; and/orj) vinyl terminated higher olefin copolymers having an Mn (measured by¹H NMR) of 300 g/mol or greater (preferably 300 to 60,000 g/mol)comprising: (i) from about 20 to 99.9 mol % of at least one C₅ to C₄₀higher olefin; and (ii) from about 0.1 to 80 mol % of propylene; whereinthe higher olefin copolymer has at least 40% allyl chain ends; and/ork) vinyl terminated higher olefin copolymers having an Mn (measured by¹H NMR) of 300 g/mol or greater (preferably 300 to 60,000 g/mol)comprising: (i) from about 80 to 99.9 mol % of at least one C₄ olefin;and (ii) from about 0.1 to 20 mol % of propylene; wherein the higherolefin copolymer has at least 40% allyl chain ends; and/orl) a higher olefin polymer having an Mn (measured by ¹H NMR) of at least200 g/mol comprising of one or more C₄ to C₄₀ higher olefin derivedunits, where the higher olefin vinyl terminated polymer comprisessubstantially no propylene derived units; and wherein the higher olefinpolymer has at least 5% allyl chain ends.10. The process of paragraph 8 or 9, wherein PO has an Mn of 300 to30,000 g/mol (as measured by ¹H NMR) comprising 10 to 90 mol % propyleneand 10 to 90 mol % of ethylene, and is derived from a vinyl terminatedpolyolefin is a polymer that has at least X % allyl chain ends (relativeto total unsaturations), where: 1) X=(−0.94 (mol % ethyleneincorporated)+100), when 10 to 60 mol % ethylene is present in thepolymer; 2) X=45, when greater than 60 and less than 70 mol % ethyleneis present in the polymer; and 3) X=(1.83*(mol % ethyleneincorporated)−83), when 70 to 90 mol % ethylene is present in thepolymer.11. The process of either paragraphs 8, 9, or 10, wherein the vinylterminated polyolefin has more than 90% allyl chain ends (relative tototal unsaturations).12. The process of either paragraphs 8 or 9, wherein the vinylterminated polyolefin comprises 15 wt % to 95 wt % ethylene and has morethan 80% allyl chain ends (relative to total unsaturations).13. The process of either paragraphs 8 or 9, wherein the vinylterminated polyolefin comprises 30 wt % to 95 wt % ethylene and has morethan 70% allyl chain ends (relative to total unsaturations).14. The process of either paragraphs 8 or 9, wherein the vinylterminated polyolefin comprises 30 wt % to 95 wt % ethylene and has morethan 90% allyl chain ends (relative to total unsaturations).15. The process of either paragraphs 8 or 9, wherein the vinylterminated polyolefin comprises a propylene oligomer comprising morethan 90 mol % propylene and less than 10 mol % ethylene, wherein theoligomer has: at least 93% allyl chain ends, an Mn of about 500 to about20,000 g/mol (as measured by ¹H NMR), an isobutyl chain end to allylicvinyl group ratio of 0.8:1 to 1.35:1.0, and less than 1400 ppm aluminum.16. The process of either paragraphs 8 or 9, wherein the vinylterminated polyolefin comprises a propylene oligomer comprising at least50 mol % propylene and from 10 to 50 mol % ethylene, wherein theoligomer has: at least 90% allyl chain ends, Mn of about 150 to about10,000 g/mol (as measured by ¹H NMR), and an isobutyl chain end toallylic vinyl group ratio of 0.8:1 to 1.3:1.0, wherein monomers havingfour or more carbon atoms are present at from 0 to 3 mol %.17. The process of either paragraphs 8 or 9, wherein the vinylterminated polyolefin comprises a propylene oligomer comprising at least50 mol % propylene, from 0.1 to 45 mol % ethylene, and from 0.1 to 5 mol% C₄ to C₁₂ olefin, wherein the oligomer has: at least 87% allyl chainends (alternately at least 90%), an Mn of about 150 to about 10,000g/mol, (as measured by ¹H NMR), and an isobutyl chain end to allylicvinyl group ratio of 0.8:1 to 1.35:1.0.18. The process of either paragraphs 8 or 9, wherein the vinylterminated polyolefin comprises a propylene oligomer comprising at least50 mol % propylene, from 0.1 to 45 mol % ethylene, and from 0.1 to 5 mol% diene, wherein the oligomer has: at least 90% allyl chain ends, an Mnof about 150 to about 10,000 g/mol (as measured by ¹H NMR), and anisobutyl chain end to allylic vinyl group ratio of 0.7:1 to 1.35:1.0.19. The process of either paragraphs 8 or 9, wherein the vinylterminated polyolefin comprises a homooligomer comprising propylene,wherein the oligomer has: at least 93% allyl chain ends, an Mn of about500 to about 20,000 g/mol (as measured by ¹H NMR), an isobutyl chain endto allylic vinyl group ratio of 0.8:1 to 1.2:1.0, and less than 1400 ppmaluminum.20. The process of any of paragraphs 8 through 19, wherein the vinylterminated polyolefin is a liquid at 25° C. and/or has a Brookfieldviscosity at 60° C. of greater than 1000 cP, greater than 12,000 cP, orgreater than 100,000 cP and preferably less than 200,000 cP, less than150,000 cP, or less than 100,000 cP.21. The process of any of paragraphs 8 through 20, wherein the Mn of thevinyl terminated polyolefin is about 500 to about 7,500 g/mol, the Mw is1,000 to about 20,000 g/mol, and the Mz is about 1400 (alternately 1700)to about 150,000 g/mol.22. The process of any of paragraphs 8 through 21, wherein the alkenemetathesis catalyst is represented by the Formula (I):

where:M is a Group 8 metal;X and X¹ are, independently, any anionic ligand, or X and X¹ may bejoined to form a dianionic group and may form single ring of up to 30non-hydrogen atoms or a multinuclear ring system of up to 30non-hydrogen atoms;L and L¹ are neutral two electron donors, L and L¹ may be joined to forma single ring of up to 30 non-hydrogen atoms or a multinuclear ringsystem of up to 30 non-hydrogen atoms;L and X may be joined to form a bidentate monoanionic group and may formsingle ring of up to 30 non-hydrogen atoms or a multinuclear ring systemof up to 30 non-hydrogen atoms;L¹ and X¹ may be joined to form a multidentate monoanionic group and mayform single ring of up to 30 non-hydrogen atoms or a multinuclear ringsystem of up to 30 non-hydrogen atoms;R and R¹ are, independently, hydrogen or C₁ to C₃₀ substituted orunsubstituted hydrocarbyl;R¹ and L¹ or X¹ may be joined to form single ring of up to 30non-hydrogen atoms or a multinuclear ring system of up to 30non-hydrogen atoms; andR and L or X may be joined to form single ring of up to 30 non-hydrogenatoms or a multinuclear ring system of up to 30 non-hydrogen atoms.23. The process of paragraph 22, wherein:M is Ru or Os;X and X¹ are, independently, a halogen, an alkoxide or a triflate, or Xand X¹ may be joined to form a dianionic group and may form single ringof up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30non-hydrogen atoms;L and L¹ are, independently, a phosphine or a N-heterocyclic carbene, Land L¹ may be joined to form a single ring of up to 30 non-hydrogenatoms or a multinuclear ring system, of up to 30 non-hydrogen atoms;L and X may be joined to form a multidentate monoanionic group and mayform single ring of up to 30 non-hydrogen atoms or a multinuclear ringsystem of up to 30 non-hydrogen atoms;L¹ and X¹ may be joined to form a multidentate monoanionic group and mayform single ring of up to 30 non-hydrogen atoms or a multinuclear ringsystem of up to 30 non-hydrogen atoms;R and R¹ are, independently, hydrogen or a C₁ to C₃₀ substituted orunsubstituted alkyl or a substituted or unsubstituted C₄ to C₃₀ aryl;R¹ and L¹ or X¹ may be joined to form single ring of up to 30non-hydrogen atoms or a multinuclear ring system of up to 30non-hydrogen atoms; andR and L or X may be joined to form single ring of up to 30 non-hydrogenatoms or a multinuclear ring system of up to 30 non-hydrogen atoms.24. The process of paragraphs 8 through 23, wherein the vinyl terminatedpolyolefin is prepared by a process having productivity of at least4.5×10³ g/mmol/hr, comprising:

contacting, at a temperature of from 35° C. to 150° C., propylene, 0.1to 70 mol % ethylene and from 0 wt % to about 5 wt % hydrogen in thepresence of a catalyst system comprising an activator and at least onemetallocene compound represented by the formulae:

whereHf is hafnium;each X is, independently, selected from the group consisting ofhydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides,alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines,ethers, or a combination thereof, preferably methyl, ethyl, propyl,butyl, phenyl, benzyl, chloride, bromide, iodide, (alternately two X'smay form a part of a fused ring or a ring system);each Q is, independently carbon or a heteroatom, preferably C, N, P, S(preferably at least one Q is a heteroatom, alternately at least two Q'sare the same or different heteroatoms, alternately at least three Q'sare the same or different heteroatoms, alternately at least four Q's arethe same or different heteroatoms);each R¹ is, independently, a C₁ to C₈ alkyl group, preferably a C₁ to C₈linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl,hexyl, heptyl, or octyl, R¹ may the same or different as R²;each R² is, independently, a C₁ to C₈ alkyl group, preferably a C₁ to C₈linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl,hexyl, heptyl, or octyl, preferably R¹ and/or R² are not branched;each R³ is, independently, hydrogen, or a substituted or unsubstitutedhydrocarbyl group having from 1 to 8 carbon atoms, preferably 1 to 6carbon atoms, preferably a substituted or unsubstituted C₁ to C₈ linearalkyl group, preferably methyl ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, provided, however, that at least three R³ groups are nothydrogen (alternately four R³ groups are not hydrogen, alternately fiveR³ groups are not hydrogen);each R⁴ is, independently, hydrogen or a substituted or unsubstitutedhydrocarbyl group, a heteroatom or heteroatom containing group,preferably a substituted or unsubstituted hydrocarbyl group having from1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, preferably asubstituted or unsubstituted C₁ to C₈ linear alkyl group, preferablymethyl ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, substitutedphenyl (such as propyl phenyl), phenyl, silyl, substituted silyl, (suchas CH₂SiR′, where R′ is a C₁ to C₁₂ hydrocarbyl, such as methyl, ethyl,propyl, butyl, phenyl);R⁵ is hydrogen or a C₁ to C₈ alkyl group, preferably a C₁ to C₈ linearalkyl group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, or octyl;R⁶ is hydrogen or a C₁ to C₈ alkyl group, preferably a C₁ to C₈ linearalkyl group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, or octyl;each R⁷ is, independently, hydrogen, or a C₁ to C₈ alkyl group,preferably a C₁ to C₈ linear alkyl group, preferably methyl ethyl,propyl, butyl, pentyl, hexyl, heptyl, or octyl, provided however that atleast seven R⁷ groups are not hydrogen, alternately at least eight R⁷groups are not hydrogen, alternately all R⁷ groups are not hydrogen,(preferably the R⁷ groups at the 3 and 4 positions on each Cp ring ofFormula IV are not hydrogen);N is nitrogen;T is a bridge, preferably, Si or Ge, preferably Si;each R^(a), is independently, hydrogen, halogen, or a C₁ to C₂₀hydrocarbyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, phenyl, benzyl, substituted phenyl, and two R^(a) canform a cyclic structure including aromatic, partially saturated, orsaturated cyclic or fused ring system; andfurther provided that any two adjacent R groups may form a fused ring ormulticenter fused ring system where the rings may be aromatic, partiallysaturated or saturated.25. The process of paragraphs 8 through 23, wherein the vinyl terminatedpolyolefins is prepared by a homogeneous process having productivity ofat least 4.5×10⁶ g/mmol/hr, comprising:

contacting, at a temperature of from 30° C. to 120° C., propylene, 0 mol% comonomer and from 0 wt % to about 5 wt % hydrogen in the presence ofa catalyst system comprising an activator and at least one metallocenecompound represented by the formulae:

whereHf is hafnium;each X is, independently, selected from the group consisting ofhydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides,alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines,ethers, or a combination thereof, preferably methyl, ethyl, propyl,butyl, phenyl, benzyl, chloride, bromide, iodide, (alternately two X'smay form a part of a fused ring or a ring system);each Q is, independently carbon or a heteroatom, preferably C, N, P, S(preferably at least one Q is a heteroatom, alternately at least two Q'sare the same or different heteroatoms, alternately at least three Q'sare the same or different heteroatoms, alternately at least four Q's arethe same or different heteroatoms);each R¹ is, independently, a C₁ to C₈ alkyl group, preferably a C₁ to C₈linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl,hexyl, heptyl, or octyl, R¹ may the same or different as R²;each R² is, independently, a C₁ to C₈ alkyl group, preferably a C₁ to C₈linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl,hexyl, heptyl, or octyl, preferably R¹ and/or R² are not branched;each R³ is, independently, hydrogen, or a substituted or unsubstitutedhydrocarbyl group having from 1 to 8 carbon atoms, preferably 1 to 6carbon atoms, preferably a substituted or unsubstituted C₁ to C₈ linearalkyl group, preferably methyl ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, provided however that: 1) all five R³ groups are methyl,or 2) four R³ groups are not hydrogen and at least one R³ group is a C₂to C₈ substituted or unsubstituted hydrocarbyl (preferably at least two,three, four or five R³ groups are a C₂ to C₈ substituted orunsubstituted hydrocarbyl);each R⁴ is, independently, hydrogen or a substituted or unsubstitutedhydrocarbyl group, a heteroatom or heteroatom containing group,preferably a substituted or unsubstituted hydrocarbyl group having from1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, preferably asubstituted or unsubstituted C₁ to C₈ linear alkyl group, preferablymethyl ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, substitutedphenyl (such as propyl phenyl), phenyl, silyl, substituted silyl, (suchas CH₂SiR′, where R′ is a C₁ to C₁₂ hydrocarbyl, such as methyl, ethyl,propyl, butyl, phenyl);R⁵ is hydrogen or a C₁ to C₈ alkyl group, preferably a C₁ to C₈ linearalkyl group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, or octyl;R⁶ is hydrogen or a C₁ to C₈ alkyl group, preferably a C₁ to C₈ linearalkyl group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, or octyl;each R⁷ is, independently, hydrogen, or a C₁ to C₈ alkyl group,preferably a C₁ to C₈ linear alkyl group, preferably methyl ethyl,propyl, butyl, pentyl, hexyl, heptyl, or octyl, provided however that atleast seven R⁷ groups are not hydrogen, alternately at least eight R⁷groups are not hydrogen, alternately all R⁷ groups are not hydrogen,(preferably the R⁷ groups at the 3 and 4 positions on each Cp ring ofFormula IV are not hydrogen);N is nitrogen;T is a bridge, preferably, Si or Ge, preferably Si;each R^(a), is independently, hydrogen, halogen or a C₁ to C₂₀hydrocarbyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, phenyl, benzyl, substituted phenyl, and two R^(a) canform a cyclic structure including aromatic, partially saturated, orsaturated cyclic or fused ring system; andfurther provided that any two adjacent R groups may form a fused ring ormulticenter fused ring system where the rings may be aromatic, partiallysaturated or saturated.26. The process of paragraphs 24 or 25, wherein the activator comprisesone or more non-coordinating anions.27. The process of paragraphs 8 through 23, wherein the vinyl terminatedpolyolefin is produced using the catalyst compound represented by theformula:

whereM is hafnium or zirconium (preferably hafnium);each X is, independently, selected from the group consisting ofhydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides,alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines,ethers, and a combination thereof, (two X's may form a part of a fusedring or a ring system) (preferably each X is independently selected fromhalides and C₁ to C₅ alkyl groups, preferably each X is a methyl group);each R⁸ is, independently, a C₁ to C₁₀ alkyl group (preferably methyl,ethyl, propyl, butyl, pentyl, hexyl, or isomers thereof, preferably eachR⁸ is a methyl group);each R⁹ is, independently, a C₁ to C₁₀ alkyl group (preferably methyl,ethyl, propyl, butyl, pentyl, hexyl, or isomers thereof, preferably eachR⁹ is a n-propyl group);each R¹⁰ is hydrogen;each R¹¹, R¹², and R¹³, is, independently, hydrogen or a substituted orunsubstituted hydrocarbyl group, a heteroatom or heteroatom containinggroup (preferably hydrogen);T is a bridging group (preferably T is dialkyl silicon or dialkylgermanium, preferably T is dimethyl silicon); andfurther provided that any of adjacent R¹¹, R¹², and R¹³ groups may forma fused ring or multicenter fused ring system where the rings may bearomatic, partially saturated or saturated; preferably by one or moreof:rac-dimethylsilyl bis(2-methyl,3-propylindenyl)hafniumdimethyl,rac-dimethylsilyl bis(2-methyl,3-propylindenyl)zirconiumdimethyl,rac-dimethylsilyl bis(2-ethyl,3-propylindenyl)hafniumdimethyl,rac-dimethylsilyl bis(2-ethyl,3-propylindenyl)zirconiumdimethyl,rac-dimethylsilyl bis(2-methyl,3-ethylindenyl)hafniumdimethyl,rac-dimethylsilyl bis(2-methyl,3-ethylindenyl)zirconiumdimethyl,rac-dimethylsilyl bis(2-methyl,3-isopropylindenyl)hafniumdimethyl,rac-dimethylsilyl bis(2-methyl,3-isopropylindenyl)zirconiumdimethyl,rac-dimethylsilyl bis(2-methyl,3-butyllindenyl)hafniumdimethyl,rac-dimethylsilyl bis(2-methyl,3-butylindenyl)zirconiumdimethyl,rac-dimethylgermanyl bis(2-methyl,3-propylindenyl)hafniumdimethyl,rac-dimethylgermanyl bis(2-methyl,3-propylindenyl)zirconiumdimethyl,rac-dimethylgermanyl bis(2-ethyl,3-propylindenyl)hafniumdimethyl,rac-dimethylgermanyl bis(2-ethyl,3-propylindenyl)zirconiumdimethyl,rac-dimethylgermanyl bis(2-methyl,3-ethylindenyl)hafniumdimethyl,rac-dimethylgermanyl bis(2-methyl,3-ethylindenyl)zirconiumdimethyl,rac-dimethylgermanyl bis(2-methyl,3-isopropylindenyl)hafniumdimethyl,rac-dimethylgermanyl bis(2-methyl,3-isopropylindenyl)zirconiumdimethyl,rac-dimethylgermanyl bis(2-methyl,3-butyllindenyl)hafniumdimethyl,rac-dimethylgermanyl bis(2-methyl,3-propylindenyl)zirconiumdimethyl,rac-dimethylsilyl bis(2-propyl,3-methylindenyl)hafniumdimethyl,rac-dimethylsilyl bis(2-propyl,3-methylindenyl)zirconiumdimethyl,rac-dimethylsilyl bis(2-propyl,3-ethylindenyl)hafniumdimethyl,rac-dimethylsilyl bis(2-propyl,3-ethylindenyl)zirconiumdimethyl,rac-dimethylsilylbis(2-propyl,3-butylindenyl)hafniumdimethyl,rac-dimethylsilylbis(2-propyl,3-butylindenyl)zirconiumdimethyl,rac-dimethylsilyl bis(2-methyl,3-butylindenyl)hafniumdimethyl,rac-dimethylsilyl bis(2-methyl,3-butylindenyl)zirconiumdimethyl,rac-dimethylsilyl bis(2,3-dimethyl)hafniumdimethyl, rac-dimethylsilylbis(2,3-dimethyl)zirconiumdimethyl, rac-dimethylgermanylbis(2-propyl,3-methylindenyl)hafniumdimethyl, rac-dimethylgermanylbis(2-propyl,3-methylindenyl)zirconiumdimethyl, rac-dimethylgermanylbis(2-propyl,3-ethylindenyl)hafniumdimethyl, rac-dimethylgermanylbis(2-propyl,3-ethylindenyl)zirconiumdimethyl, rac-dimethylgermanylbis(2-propyl,3-butylindenyl)hafniumdimethyl, rac-dimethylgermanylbis(2-propyl,3-butylindenyl)zirconiumdimethyl, rac-dimethylgermanylbis(2-methyl,3-butylindenyl)hafniumdimethyl, rac-dimethylgermanylbis(2-methyl,3-butylindenyl)zirconiumdimethyl, rac-dimethylgermanylbis(2,3-dimethyl)hafniumdimethyl, and rac-dimethylgermanylbis(2,3-dimethyl)zirconiumdimethyl, alternately the “dimethyl” after thetransition metal in the list of catalyst compounds above is replacedwith a dihalide (such as dichloride or difluoride) or a bisphenoxide,particularly for use with an alumoxane activator.28. The process of paragraphs 8 through 23, wherein the vinyl terminatedpolyolefin is produced using the catalyst compound represented by theformula:

whereinM is hafnium or zirconium;each X is, independently, selected from the group consisting ofhydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides,alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines,ethers, or a combination thereof;each R¹⁵ and R¹⁷ are, independently, a C₁ to C₈ alkyl group (preferablya C₁ to C₈ linear alkyl group, preferably methyl ethyl, propyl, butyl,pentyl, hexyl, heptyl, or octyl); andeach R¹⁶, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, each R²⁸are, independently, hydrogen, or a substituted or unsubstitutedhydrocarbyl group having from 1 to 8 carbon atoms (preferably 1 to 6carbon atoms, preferably a substituted or unsubstituted C₁ to C₈ linearalkyl group, preferably methyl ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl), preferably at least three of R²⁴-R²⁸ groups are nothydrogen (alternately four of R²⁴-R²⁸ groups are not hydrogen,alternately five of R²⁴-R²⁸ groups are not hydrogen), preferably allfive groups of R²⁴-R²⁸ are methyl, preferably four of the R²⁴-R²⁸ groupsare not hydrogen and at least one of the R²⁴-R²⁸ groups is a C₂ to C₈substituted or unsubstituted hydrocarbyl (preferably at least two,three, four or five of R²⁴-R²⁸ groups are a C₂ to C₈ substituted orunsubstituted hydrocarbyl), preferably R¹⁵ and R¹⁷ are methyl groups,R¹⁶ is a hydrogen, R¹⁸-R²³ are all hydrogens, R²⁴-R²⁸ are all methylgroups, and each X is a methyl group, preferably the catalyst compoundis one or more of (CpMe₅)(1,3-Me₂-benz[e]indenyl)HfMe₂,(CpMe₅)(1-methyl-3-n-propylbenz[e] indenyl)HfMe₂,(CpMe₅)(1-n-propyl,3-methylbenz[e] indenyl)HfMe₂,(CpMe₅)(1-methyl-3-n-butylbenz[e] indenyl)HfMe₂,(CpMe₅)(1-n-butyl,3-methylbenz[e] indenyl)HfMe₂,(CpMe₅)(1-ethyl,3-methylbenz[e] indenyl)HfMe₂, (CpMe₅)(1-methyl,3-ethylbenz[e] indenyl)HfMe₂, (CpMe₄n-propyl)(1,3-Me₂-benz[e]indenyl)HfMe₂, (CpMe₄-n-propyl)(1-methyl-3-n-propylbenz[e]indenyl)HfMe₂,(CpMe₄-n-propyl)(1-n-propyl,3-methylbenz[e] indenyl)HfMe₂,(CpMe₄-n-propyl)(1-methyl-3-n-butylbenz[e] indenyl)HfMe₂,(CpMe₄-n-propyl)(1-n-butyl,3-methylbenz[e] indenyl)HfMe₂,(CpMe₄-n-propyl)(1-ethyl,3-methylbenz[e] indenyl)HfMe₂,(CpMe₄-n-propyl)(1-methyl, 3-ethylbenz[e] indenyl)HfMe₂,(CpMe₄n-butyl)(1,3-Me₂-benz[e] indenyl)HfMe₂,(CpMe₄n-butyl)(1-methyl-3-n-propylbenz[e]indenyl)HfMe₂,(CpMe₄n-butyl)(1-n-propyl,3-methylbenz[e] indenyl)HfMe₂,(CpMe₄n-butyl)(1-methyl-3-n-butylbenz[e] indenyl)HfMe₂,(CpMe₄n-butyl)(1-n-butyl,3-methylbenz[e] indenyl)HfMe₂,(CpMe₄n-butyl)(1-ethyl,3-methylbenz[e] indenyl)HfMe₂,(CpMe₄n-butyl)(1-methyl, 3-ethylbenz[e]indenyl)HfMe₂, and the zirconiumanalogs thereof, alternately the “dimethyl” (Me₂) after the transitionmetal in the list of catalyst compounds above is replaced with adihalide (such as dichloride or difluoride) or a bisphenoxide,particularly for use with an alumoxane activator.29. The process of any of paragraphs 8 to 28, wherein the activator is abulky activator represented by the formula:

whereeach R₁ is, independently, a halide, preferably a fluoride;each R₂ is, independently, a halide, a C₆ to C₂₀ substituted aromatichydrocarbyl group or a siloxy group of the formula —O—Si—R_(a), whereR_(a) is a C₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl group (preferablyR₂ is a fluoride or a perfluorinated phenyl group);each R₃ is a halide, C₆ to C₂₀ substituted aromatic hydrocarbyl group ora siloxy group of the formula —O—Si—R_(a), where R_(a) is a C₁ to C₂₀hydrocarbyl or hydrocarbylsilyl group (preferably R₃ is a fluoride or aC₆ perfluorinated aromatic hydrocarbyl group); wherein R₂ and R₃ canform one or more saturated or unsaturated, substituted or unsubstitutedrings (preferably R₂ and R₃ form a perfluorinated phenyl ring);L is an neutral Lewis base; (L-H)⁺ is a Bronsted acid; d is 1, 2, or 3;wherein the anion has a molecular weight of greater than 1020 g/mol; andwherein at least three of the substituents on the B atom each have amolecular volume of greater than 250 cubic Å, alternately greater than300 cubic Å, or alternately greater than 500 cubic Å,30. The process of any of paragraphs 8 to 28, wherein the activator isone or more of: trimethylammonium tetrakis(perfluoronaphthyl)borate,triethylammonium tetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,tropillium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate,benzene(diazonium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,tropillium tetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate,benzene(diazonium)tetrakis(perfluorobiphenyl)borate,[4-t-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B], and the types disclosed in U.S.Pat. No. 7,297,653.31. The process of paragraphs 8 through 30, wherein the activatorcomprises one or more of:dimethylaniliniumtetrakis(pentafluorophenyl)borate,dimethylaniliniumtetrakis(heptafluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,tropillium tetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate,benzene(diazonium)tetrakis(perfluorobiphenyl)borate, and[4-t-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B] (where Ph is phenyl and Me ismethyl).

EXAMPLES Tests and Materials

Products were characterized by ¹H NMR and DSC as follows.

¹H NMR

¹H NMR data was collected at either room temperature or 120° C. (forpurposes of the claims, 120° C. shall be used) in a 5 mm probe using aVarian spectrometer with a ¹Hydrogen frequency of at least 400 MHz. Datawas recorded using a maximum pulse width of 45°, 8 seconds betweenpulses and signal averaging 120 transients. Spectral signals wereintegrated and the number of unsaturation types per 1000 carbons wascalculated by multiplying the different groups by 1000 and dividing theresult by the total number of carbons.

DSC

Melting temperature (T_(m)) and glass transition temperature (Tg) aremeasured using Differential Scanning calorimetry (DSC) usingcommercially available equipment such as a TA Instruments 2920 DSC.Typically, 6 to 10 mg of the sample, that has been stored at roomtemperature for at least 48 hours, is sealed in an aluminum pan andloaded into the instrument at room temperature. The sample isequilibrated at 25° C., and then it is cooled at a cooling rate of 10°C./min to −80° C. The sample is held at −80° C. for 5 min and thenheated at a heating rate of 10° C./min to 25° C. The glass transitiontemperature is measured from the heating cycle. Alternatively, thesample is equilibrated at 25° C., and then heated at a heating rate of10° C./min to 150° C. The endothermic melting transition, if present, isanalyzed for onset of transition and peak temperature. The meltingtemperatures reported are the peak melting temperatures from the firstheat unless otherwise specified. For samples displaying multiple peaks,the melting point (or melting temperature) is defined to be the peakmelting temperature (i.e., associated with the largest endothermiccalorimetric response in that range of temperatures) from the DSCmelting trace.

All molecular weights are number average unless otherwise noted. AllMolecular weights are reported in g/mol.

The following abbreviations are used in the Examples:

aPP is atactic polypropylene, iPP is isotactic polypropylene, EP isethylene-propylene copolymer, TCE is 1,1,2,2-tetrachloroethane, h ishours, min is minutes, M_(n) is the number average molecular weight asdetermined by ¹H NMR spectroscopy by comparison of integrals of thealiphatic region to the olefin region as determined using the protocoldescribed in the Experimental section of WO2009/155471, Zhan 1B is1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(1-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II)dichloride.

Example 1 Synthesis of PE-PEG-PE Triblock

1-Eicosene (1.08 g, 3.84 mmol), poly(ethylene glycol)diacrylate (1.59 g,2.05 mmol) with an estimated Mn of 777 g/mol, and Zhan 1B (0.0175 g,0.0239 mmol) were combined in a vial. Then pentane (4 mL) anddichloromethane (4 mL) were added to form a homogeneous mixture that washeated on a metal block kept at 45° C. Additional pentane was addedperiodically as the mixture evaporated for a few hours. The mixture waskept at 39° C. overnight. At this time ¹H NMR spectroscopy indicatedthat 94% of the acrylate groups had undergone cross metathesis witheicosene with loss of ethylene. The reaction was quenched by theaddition of a few drops of ethyl vinyl ether. Pentane (100 mL) was addedand the mixture was passed slowly down a column of neutral alumina, withsome loss of product that precipitated on the column. The volatiles wereremoved under vacuum to afford the product as a white solid. Yield: 1.2g. ¹H NMR (250 MHz, CDCl₃): δ 6.97 (dt, 2.0H), 5.82 (d, 2.1H), 4.29(pseudo t, 4.4H), 3.70 (pseudo t, 4.4; H), 3.62 (m, 42.7H), 2.17 (q,4.0H), 1.63 (s, 2.4H, water), 1.1-1.5 (m, 69.2H), 0.86 (t, 6.7H).

where n is about 15.

Example 2 Synthesis of PE-PEG Diblock

1-Eicosene (2.38 g, 8.48 mmol) and poly(ethylene glycol) methyl etheracrylate (4.47 g, 8.48 mmol) with an estimated Mn of 527 g/mol werecombined in a vial. Dichloromethane (8 mL) was added followed by solidZhan 1B (0.062 g, 0.0848 mmol) and some pentane (5 mL). The mixture waskept near reflux on a metal block kept at 39° C. After stirringovernight a few drops of ethyl vinyl ether were added. After 0.5 h thevolatiles were removed and pentane (100 mL) was added. This mixture wasslowly passed through neutral alumina. Removal of the volatiles affordedthe diblock product as a white semi solid. Yield 2.53 g. ¹H NMR (500MHz, CDCl₃): δ 6.96 (dt, 1.0H), 5.81 (d, 1.0H), 4.29 (m, 2.0H), 3.70 (m,2.0H), 3.62 (m, 21.3H), 3.51 (m, 1.8H), 3.35 (s, 2.7H), 2.16 (q, 2.0H),1.15-1.46 (m, 35.8H), 0.85 (t, 3.3H).

where n=about 10.

Example 3 Synthesis of ^(i)PP-PEG diblock

Isotactic polypropylene (4.29 g, 0.361 mmol) with an M_(n) of 11900 and85% vinyl termination was combined with toluene (40 mL), and the mixturewas heated to 100° C. to form a clear colorless solution. The mixturewas cooled to about 65° C. and poly(ethylene glycol) methyl etheracrylate (0.500 g, 0.948 mmol) with an estimated M_(n) of 527 anddichloromethane (10 mL) were added followed by Zhan 1B (0.0265 g, 0.0361mmol). The mixture was kept at 60° C. overnight then poured intostirring methanol (300 mL). The white solid was collected on a frit andthoroughly washed with methanol. The product was dried at 70° C. underreduced pressure for 3 days. Yield 4.27 g. NMR analysis indicatedabsence of vinyl groups and the formation of the PP-PEG block productand about 0.2 molar equivalents of an impurity thought to be thehomocoupled PEG-acrylate (i.e.,(MeO(CH₂CH₂O)_(n)—C(O)CH═CHC(O)(OCH₂CH₂)_(n)OMe). ¹H NMR (500 MHz,D₄-tetrachloroethane): δ 6.99 (dt, 1.0H), 6.90 (s, 0.4H, impurity), 5.87(d, 1.2H), 4.39 (t, 0.9H, impurity), 4.30 (t, 2H), 3.5-3.8 (m, 68.8H),3.40 (s, 5.7H, product and impurity), 0.8-1.8 (m, 3080H).

where n is about 10.

All documents described herein are incorporated by reference herein forpurposes of all jurisdictions where such practice is allowed, includingany priority documents, related applications and/or testing proceduresto the extent they are not inconsistent with this text, provided howeverthat any priority document not named in the initially filed applicationor filing documents is NOT incorporated by reference herein. As isapparent from the foregoing general description and the specificembodiments, while forms of the invention have been illustrated anddescribed, various modifications can be made without departing from thespirit and scope of the invention. Accordingly, it is not intended thatthe invention be limited thereby. Likewise, the term “comprising” isconsidered synonymous with the term “including” for purposes ofAustralian law. Likewise whenever a composition, an element or a groupof elements is preceded with the transitional phrase “comprising,” it isunderstood that we also contemplate the same composition or group ofelements with transitional phrases “consisting essentially of,”“consisting of,” “selected from the group of consisting of,” or “is”preceding the recitation of the composition, element, or elements andvice versa.

What is claimed is:
 1. A process to prepare a multiblock polyolefinrepresented by the formula (X) or (XX):PO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(O)—O—((CR¹⁵R¹⁶)_(z)—(CR¹⁷R¹⁸)_(m)—O)_(n)—R¹⁹  (X)orPO—C(R¹¹)(R¹²)—C(R¹³)═C(R¹⁴)—C(O)—O—((CR¹⁵R¹⁶)_(z)—(CR¹⁷R¹⁸)_(m)O)_(n)—C(O)—C(R¹⁴)═C(R¹³)—C(R¹²)(R¹¹)—PO  (XX),wherein R¹¹, R¹², R¹³, and R¹⁴ are each independently a substituted orunsubstituted C₁ through C₄ hydrocarbyl group or a hydrogen; R¹⁵, R¹⁶,R¹⁷, and R¹⁸ are each independently a substituted or unsubstituted C₁through C₄ hydrocarbyl group or a hydrogen; R¹⁹ is a C₁ to a C₂₀substituted or unsubstituted hydrocarbyl group or a hydrogen; z is ≧1 toabout 5; m is ≧1 to about 5; PO is a polyolefin hydrocarbyl groupcomprising 10 to 4000 carbon atoms; n is from 1 to about 10,000;comprising contacting an alkene metathesis catalyst with i) a vinylterminated polyolefin containing at least 5% allyl chain ends (relativeto total unsaturations), and ii) an acrylate or methacrylatefunctionalized polyalkylene glycol represented by the formula (XII) or(XXII):C(R¹³)(R²⁰)═C(R¹⁴)—C(O)—O—((CR¹⁵R¹⁶)_(z)—(CR¹⁷R¹⁸)_(m)—O)_(n)—R¹⁹  (XII)orC(R¹³)(R²⁰)═C(R¹⁴)—C(O)—O—((CR¹⁵R¹⁶)_(z)—(CR¹⁷R¹⁸)_(m)—(O)_(n)—C(O)—C(R¹⁴)═C(R¹³)(R²⁰)  (XXII)wherein R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, Z, M, and N are as definedabove; R²⁰ is a hydrogen or a C₁ to a C₄ substituted or unsubstitutedhydrocarbyl group.
 2. The process of claim 1, wherein the vinylterminated polyolefin has an Mn of 300 to 30,000 g/mol (as measured by¹H NMR) comprising 10 to 90 mol % propylene and 10 to 90 mol % ofethylene, wherein the polyolefin has at least X % allyl chain ends(relative to total unsaturations), where: 1) X=(−0.94 (mol % ethyleneincorporated)+100), when 10 to 60 mol % ethylene is present in thepolyolefin, and 2) X=45, when greater than 60 and less than 70 mol %ethylene is present in the polyolefin, and 3) X=(1.83*(mol % ethyleneincorporated)−83), when 70 to 90 mol % ethylene is present in thepolyolefin.
 3. The process of claim 1, wherein the vinyl terminatedpolyolefin has more than 90% allyl chain ends (relative to totalunsaturations).
 4. The process of claim 1, wherein the vinyl terminatedpolyolefin comprises 15 wt % to 95 wt % ethylene and has more than 80%allyl chain ends (relative to total unsaturations).
 5. The process ofclaim 1, wherein the vinyl terminated polyolefin comprises 30 wt % to 95wt % ethylene and has more than 70% allyl chain ends (relative to totalunsaturations).
 6. The process of claim 1, wherein the vinyl terminatedpolyolefin comprises 30 wt % to 95 wt % ethylene and has more than 90%allyl chain ends (relative to total unsaturations).
 7. The process ofclaim 1, wherein the vinyl terminated polyolefin comprises a propyleneoligomer comprising more than 90 mol % propylene and less than 10 mol %ethylene, wherein the oligomer has: at least 93% allyl chain ends, an Mnof about 500 to about 20,000 g/mol (as measured by ¹H NMR), an isobutylchain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0, and lessthan 1400 ppm aluminum.
 8. The process of claim 1, wherein the vinylterminated polyolefin comprises a propylene oligomer comprising at least50 mol % propylene and from 10 to 50 mol % ethylene, wherein theoligomer has: at least 90% allyl chain ends, Mn of about 150 to about10,000 g/mol (as measured by ¹H NMR), and an isobutyl chain end toallylic vinyl group ratio of 0.8:1 to 1.3:1.0, wherein monomers havingfour or more carbon atoms are present at from 0 to 3 mol %.
 9. Theprocess of claim 1, wherein the vinyl terminated polyolefin comprises apropylene oligomer comprising at least 50 mol % propylene, from 0.1 to45 mol % ethylene, and from 0.1 to 5 mol % C₄ to C₁₂ olefin, wherein theoligomer has: at least 87% allyl chain ends (alternately at least 90%),an Mn of about 150 to about 10,000 g/mol, (as measured by ¹H NMR), andan isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0.10. The process of claim 1, wherein the vinyl terminated polyolefincomprises a propylene oligomer comprising at least 50 mol % propylene,from 0.1 to 45 mol % ethylene, and from 0.1 to 5 mol % diene, whereinthe oligomer has: at least 90% allyl chain ends, an Mn of about 150 toabout 10,000 g/mol (as measured by ¹H NMR), and an isobutyl chain end toallylic vinyl group ratio of 0.7:1 to 1.35:1.0.
 11. The process of claim1, wherein the vinyl terminated polyolefin comprises a homooligomercomprising propylene, wherein the oligomer has: at least 93% allyl chainends, an Mn of about 500 to about 20,000 g/mol (as measured by ¹H NMR),an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.2:1.0,and less than 1400 ppm aluminum.
 12. The process of claim 1, wherein thevinyl terminated polyolefin comprises a branched polyolefin having an Mn(¹H NMR) of 7,500 to 60,000 g/mol comprising: (i) one or more alphaolefin derived units comprising ethylene and propylene; (ii) 50% orgreater allyl chain ends, relative to total number of unsaturated chainends; and (iii) a g′(vis) of 0.90 or less.
 13. The process of claim 1,wherein the vinyl terminated polyolefin comprises a branched polyolefinhaving an Mn greater than 60,000 g/mol comprising: (i) one or more alphaolefins comprising ethylene and propylene; (ii) 50% or greater allylchain ends, relative to total unsaturated chain ends; (iii) a g′(vis) of0.90 or less; and (iv) a bromine number which, upon completehydrogenation, decreases by at least 50%.
 14. The process of claim 1,wherein the vinyl terminated polyolefin comprises a branched polyolefinhaving an Mn of less than 7,500 g/mol comprising: (i) one or more alphaolefin derived units comprising ethylene and propylene; (ii) a ratio ofpercentage of saturated chain ends to percentage of allyl chain ends of1.2 to 2.0; and (iii) 50% or greater allyl chain ends, relative to totalmoles of unsaturated chain ends.
 15. The process of claim 1, wherein thevinyl terminated polyolefin comprises a vinyl terminated higher olefincopolymer having an Mn (measured by ¹H NMR) of 300 g/mol or greatercomprising: (i) from about 20 to 99.9 mol % of at least one C₅ to C₄₀higher olefin; and (ii) from about 0.1 to 80 mol % of propylene; whereinthe higher olefin copolymer has at least 40% allyl chain ends.
 16. Theprocess of claim 1, wherein the vinyl terminated polyolefin comprisevinyl terminated higher olefin copolymers having an Mn (measured by ¹HNMR) of 300 g/mol or greater comprising: (i) from about 80 to 99.9 mol %of at least one C₄ olefin; and (ii) from about 0.1 to 20 mol % ofpropylene; wherein the higher olefin copolymer has at least 40% allylchain ends.
 17. The process of claim 1, wherein the vinyl terminatedpolyolefin comprises a higher olefin polymer having an Mn (measured by¹H NMR) of at least 200 g/mol comprising of one or more C₄ to C₄₀ higherolefin derived units, where the higher olefin vinyl terminated polymercomprises substantially no propylene derived units; and wherein thehigher olefin polymer has at least 5% allyl chain ends.
 18. The processof claim 1, wherein the vinyl terminated polyolefin is a liquid at 25°C.
 19. The process of claim 1, wherein the Mn of the vinyl terminatedpolyolefin is about 500 to about 7,500 g/mol, the Mw is 1,000 to about20,000 g/mol, and the Mz is about 1400 to about 150,000 g/mol.
 20. Theprocess of claim 1, wherein the alkene metathesis catalyst isrepresented by the Formula (I):

where: M is a Group 8 metal; X and X¹ are, independently, any anionicligand, or X and X¹ may be joined to form a dianionic group and may formsingle ring of up to 30 non-hydrogen atoms or a multinuclear ring systemof up to 30 non-hydrogen atoms; L and L¹ are neutral two electrondonors, L and L¹ may be joined to form a single ring of up to 30non-hydrogen atoms or a multinuclear ring system of up to 30non-hydrogen atoms; L and X may be joined to form a bidentatemonoanionic group and may form single ring of up to 30 non-hydrogenatoms or a multinuclear ring system of up to 30 non-hydrogen atoms; L¹and X¹ may be joined to form a multidentate monoanionic group and mayform single ring of up to 30 non-hydrogen atoms or a multinuclear ringsystem of up to 30 non-hydrogen atoms; R and R¹ are, independently,hydrogen or C₁ to C₃₀ substituted or unsubstituted hydrocarbyl; R¹ andL¹ or X¹ may be joined to form single ring of up to 30 non-hydrogenatoms or a multinuclear ring system of up to 30 non-hydrogen atoms; andR and L or X may be joined to form single ring of up to 30 non-hydrogenatoms or a multinuclear ring system of up to 30 non-hydrogen atoms.